Stabilized nanoparticle compositions comprising ions

ABSTRACT

A composition including a coated nanoparticle and an ion, wherein the coated nanoparticle includes a nanoparticle, a linker, and a stabilizing group; methods of making and using the composition; and systems including the composition. The linker includes an anchoring group, a spacer, and a terminal group. The anchoring group is covalently bound to the nanoparticle and at least one of the terminal groups is covalently bound to at least one stabilizing group. A composition including a crosslinked-coated nanoparticle and an ion, wherein the crosslinked-coated nanoparticle includes a nanoparticle and a coating that includes a linker, a crosslinker, and a stabilizing group; methods of making and using the composition; and systems including the composition.

TECHNICAL FIELD

This application is a continuation of U.S. patent application Ser. No.15/205,869 filed Jul. 8, 2016 and claims the benefit of the filing dateof U.S. Provisional Application Ser. No. 62/191,871 filed Jul. 13, 2015.The contents of U.S. Provisional Application Ser. No. 62/191,871 andU.S. patent application Ser. No. 15/205,869 are incorporated byreference in their entirety as part of this application.

TECHNICAL FIELD

This document relates to methods and compositions used in treatingsubterranean formations for enhancing hydrocarbon fluid recovery.

SUMMARY

Provided in this disclosure is a method of treating a subterraneanformation. The method includes placing in a subterranean formation acomposition including a coated nanoparticle and an ion. The coatednanoparticle includes a nanoparticle, a linker, and a stabilizing group.The linker includes an anchoring group, a spacer, and a terminal group.Further, the anchoring group is covalently bound to the nanoparticle andat least one of the terminal groups is covalently bound to at least onestabilizing group.

In some embodiments, the composition further includes an aqueous liquid.The aqueous liquid can include at least one of water, brine, producedwater, flowback water, brackish water, fresh water, Arab-D-brine, seawater, mineral waters, and other waters of varying salinity and mineralconcentration. The aqueous liquid can include at least one of a drillingfluid, a fracturing fluid, a diverting fluid, an injection fluid, and alost circulation treatment fluid.

In some embodiments, method further includes obtaining or providing thecomposition. The obtaining or providing of the composition can occurabove-surface. The obtaining or providing of the composition can occurin the subterranean formation.

In some embodiments, the method is a method of drilling the subterraneanformation. In some embodiments, the method is a method of fracturing thesubterranean formation. In some embodiments, the method is a method ofconformance control. In some embodiments, the method is a method ofsubsurface imaging the subterranean formation. In some embodiments, themethod is a method of aquifer remediation in the subterranean formation.

In some embodiments, the coated nanoparticles have a lower criticalsolution temperature (“LCST”) of greater than 90° C.

In some embodiments, the coated nanoparticles have a hydrodynamic radiusof less than about 100 nanometers (nm). In some embodiments, the coatednanoparticles, when at a concentration of about 2,000 parts per million(ppm, as used herein 1 ppm is equal to 1 mg/L) in synthetic sea water,have a hydrodynamic radius of less than about 250 nm after heating at90° C. in the synthetic sea water for 8 days. In some embodiments, thecoated nanoparticles, when at a concentration of about 2,000 ppm insynthetic Arab-D brine, have a hydrodynamic radius of less than about250 nm after heating at 90° C. in the synthetic Arab-D brine at aconcentration of 2,000 ppm for 8 days. In some embodiments, the coatednanoparticles, when at a concentration of about 1,000 ppm in syntheticArab-D brine, have a hydrodynamic radius of less than about 250 nm afterheating at 90° C. in the synthetic Arab-D brine at a concentration of1,000 ppm for 8 days.

In some embodiments, the coated nanoparticles have a hydrodynamic radiusthat is less than the hydrodynamic radius of similar nanoparticleswithout the one or more stabilizing groups in a similar compositionunder similar conditions. For example, the coated nanoparticles can havea hydrodynamic radius that is less than the hydrodynamic radius ofsimilar nanoparticles without the one or more stabilizing groups in asimilar composition in synthetic sea water or synthetic Arab-D brine.

In some embodiments, the nanoparticle is selected from the groupconsisting of a silica nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andmixtures thereof. In some embodiments, the nanoparticle can include ametal oxide. For example, the nanoparticle can include a magnetic metaloxide. In some embodiments, the nanoparticle includes an iron oxide, anickel oxide, a cobalt oxide, a magnetite, a ferrite, or combinationsthereof. In some embodiments, the nanoparticle includes a metal oxideincluding an atom selected from the group consisting of Zn, Cr, Co, Dy,Er, Eu, Fe, Gd, Gd, Pr, Nd, Ni, In, Pr, Sm, Tb, Tm, and combinationsthereof. In some embodiments, the nanoparticle is a silica nanoparticle.For example, the nanoparticle can be a fluorescent silica nanoparticle.

In some embodiments, the nanoparticles have an average particle size ofabout 10 nm to about 100 nm.

In some embodiments, the linker includes polyethylenimine. For example,the nanoparticle and covalently bound linker can be obtained by reactingtrimethoxysilylpropyl modified polyethylenimine with the nanoparticle.

In some embodiments, the linker spacer includes the subunit:

The variable R¹ can be selected from the from the group consisting of—H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 indicates a point of attachment to another linker on thecoated nanoparticle. The variable A is a (C₁-C₁₀)alkyl interrupted with0, 1, 2, 3, or 4 oxygen atoms or substituted or unsubstituted nitrogenatoms.

In some embodiments, the linker terminal group is —OR^(A) ₂, —SR^(A) ₂,—N—NR^(A) ₂, O—NR^(A) ₂, or NR^(A) ₂. The variable R^(A), at eachoccurrence is independently selected from —H or

The wavy line labeled 2 indicates a point of attachment to thestabilizing group.

In some embodiments, the stabilizing group includes one or more of —OH,—CO₂H, —CO₂CH₃, a phosphonate, a phosphate, a sulfonate, or a sulfate.For example, the stabilizing group can include a functional groupselected from group consisting of:

and combinations thereof.The wavy line indicates a point of attachment to the linker terminalgroup.

In some embodiments, the coated nanoparticles have a positive zetapotential.

In some embodiments, about 5% to about 95% of terminal groups arecovalently bound to a stabilizing group.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the providing or obtaining the composition includesdetermining the presence and concentration of at least one ion of awater in a subterranean formation and doping the composition with thedetermined ion. The method can further include determining theconcentration of the at least one ion of the water in the subterraneanformation and increasing the amount of the determined ion in thecomposition such that molarity of the determined ion in the compositionis at least 10% of the molarity of the at least one ion of the water inthe subterranean formation.

In some embodiments, the composition further includes a kosmotropic ion.The method can further include aggregating, or aggregating andprecipitating the coated nanoparticles in the subterranean formation bythe addition of a kosmotropic ion.

In some embodiments, the composition further includes a chaotropic ion.

In some embodiments, the method further includes combining thecomposition with an aqueous or oil-based fluid including a drillingfluid, a stimulation fluid, fracturing fluid, a spotting fluid, aclean-up fluid, a completion fluid, a remedial treatment fluid, anabandonment fluid, a pill, an acidizing fluid, a cementing fluid, apacker fluid, an imaging fluid or a combination thereof, to form amixture, in which the placing the composition in the subterraneanformation includes placing the mixture in the subterranean formation.

In some embodiments, at least one of prior to, during, and after theplacing of the composition in the subterranean formation, thecomposition is used in the subterranean formation, at least one of aloneand in combination with other materials, as a drilling fluid, astimulation fluid, a fracturing fluid, a spotting fluid, a clean-upfluid, a completion fluid, a remedial treatment fluid, an abandonmentfluid, a pill, an acidizing fluid, a cementing fluid, a packer fluid, animaging fluid, or a combination thereof.

In some embodiments, the composition further includes a saline, anaqueous base, an oil, an organic solvent, a synthetic fluid oil phase,an aqueous solution, an alcohol or a polyol, a cellulose, a starch, analkalinity control agent, an acidity control agent, a density controlagent, a density modifier, an emulsifier, a dispersant, a polymericstabilizer, a crosslinking agent, a polyacrylamide, a polymer, anantioxidant, a heat stabilizer, a foam control agent, a foaming agent, asolvent, a diluent, a plasticizer, a filler, an inorganic particle, apigment, a dye, a precipitating agent, a rheology modifier, anoil-wetting agent, a set retarding additive, a surfactant, a corrosioninhibitor, a gas, a weight reducing additive, a heavy-weight additive, alost circulation material, a filtration control additive, a salt, afiber, a thixotropic additive, a breaker, a crosslinker, a gas, arheology modifier, a curing accelerator, a curing retarder, a pHmodifier, a chelating agent, a scale inhibitor, an enzyme, a resin, awater control material, a polymer, an oxidizer, a marker, a Portlandcement, a pozzolana cement, a gypsum cement, a high alumina contentcement, a slag cement, a silica cement, a fly ash, a metakaolin, ashale, a zeolite, a crystalline silica compound, an amorphous silica, afiber, a hydratable clay, a microsphere, a pozzolan lime, orcombinations thereof.

In some embodiments, placing the composition in the subterraneanformation includes fracturing at least part of the subterraneanformation to form at least one subterranean fracture.

In some embodiments, the composition further includes a proppant, aresin-coated proppant, or a combination thereof.

In some embodiments, the placing of the composition in the subterraneanformation includes pumping the composition through a drill stringdisposed in a wellbore, through a drill bit at a downhole end of thedrill string, and back above-surface through an annulus. The method canfurther include, processing the composition exiting the annulus with atleast one fluid processing unit to generate a cleaned composition andrecirculating the cleaned composition through the wellbore.

Also, provided in this disclosure is a method of treating a subterraneanformation, the method including (i) placing in a subterranean formationa composition including (a) a coated nanoparticle including a silicananoparticle, a linker, and a stabilizing group, and (b) a calcium ion.The linker includes a silane anchoring group and polyethylenimine. Thestabilizing group includes a propyl 1,2 diol. Further, the linker iscovalently bound to the nanoparticle and at least one amine of thepolyethylenimine is covalently bound to the propyl 1,2 diol stabilizinggroup.

Also, provided in this disclosure is a coated nanoparticle compositionincluding (i) a coated nanoparticle including a nanoparticle, a linker,and a stabilizing group and (ii) an ion. The linker includes a silaneanchoring group, a spacer, and a terminal group. Further, the silaneanchoring group is covalently bound to the nanoparticle core and atleast one of the terminal groups is covalently bound to at least onestabilizing group.

In some embodiments, the composition further includes an aqueous liquidincluding one or more of water, brine, produced water, flowback water,brackish water, fresh water, Arab-D-brine, sea water, mineral waters,and other waters of varying salinity and mineral concentration.

In some embodiments, the nanoparticle is selected from the groupconsisting of a silica nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andmixtures thereof. The nanoparticle can be a silica nanoparticle. Thelinker can include polyethylenimine. The stabilizing group can include afunctional group selected from the group consisting of:

and combinations thereof. The wavy line indicates a point of attachmentto the linker terminal group.

The ion can include one or more of a lithium ion, a sodium ion, apotassium ion, a silver ion, a magnesium ion, a calcium ion, a bariumion, a zinc ion, an aluminum ion, a bismuth ion, a copper (I) ion, acopper (II) ion, an iron (II) ion, an iron (III) ion, a tin (II) ion, atin (IV) ion, a chromium (II) ion, a chromium (III) ion, a manganese(II) ion, a manganese (III) ion, a mercury (I) ion, a mercury (II) ion,a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt (III) ion,a nickel ion (II), a nickel (IV) ion, a titanium ion, and a titanium(IV) ion. For example, the ion can include a calcium ion. Also providedin this disclosure, is a coated nanoparticle composition including (i) acoated nanoparticle including a silica nanoparticle, a linker, and astabilizing group, and (ii) a calcium ion. The linker includes a silaneanchoring group and polyethylenimine. The stabilizing group includes apropyl 1,2 diol. Further, the linker is covalently bound to thenanoparticle and at least one amine of the polyethylenimine iscovalently bound to the propyl 1,2 diol stabilizing group

Also provided in this disclosure, is a coated nanoparticle including (i)a nanoparticle, (ii) a linker including a silane anchoring group, aspacer, and a terminal group, and (iii) a stabilizing group. The silaneanchoring group is covalently bound to the nanoparticle core and atleast one of the terminal groups is covalently bound to the stabilizinggroup.

Also, provided in this disclosure is a coated nanoparticle including (i)a silica nanoparticle (ii) a linker including a silane anchoring groupand polyethylenimine, and (iii) a stabilizing group including propyl 1,2diol. The linker is covalently bound to the nanoparticle and at leastone amine of the polyethylenimine is covalently bound to the propyl 1,2diol stabilizing group.

Also provided herein is a method of treating a subterranean formation,the method including placing in a subterranean formation a compositionincluding an ion and a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The coating includes a linker, a crosslinker, and a stabilizing group.

The ion can include one or more of a lithium ion, a sodium ion, apotassium ion, a silver ion, a magnesium ion, a calcium ion, a bariumion, a zinc ion, an aluminum ion, a bismuth ion, a copper (I) ion, acopper (II) ion, an iron (II) ion, an iron (III) ion, a tin (II) ion, atin (IV) ion, a chromium (II) ion, a chromium (III) ion, a manganese(II) ion, a manganese (III) ion, a mercury (I) ion, a mercury (II) ion,a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt (III) ion,a nickel ion (II), a nickel (IV) ion, a titanium ion, and a titanium(IV) ion. In some embodiments, the ion includes a calcium ion.

The linker can be crosslinked with the crosslinker. The stabilizinggroup can be covalently bound to the linker. In some embodiments, thelinker is crosslinked with the crosslinker and the linker is covalentlybound to the stabilizing group.

In some embodiments, the linker includes the subunit:

At each occurrence, the variable R¹ can be independently selected fromthe from the group consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canindependently selected from a (C₁-C₁₀)alkyl interrupted with 0, 1, 2, 3,or 4 oxygen atoms or substituted or unsubstituted nitrogen atoms.

In some embodiments, the linker includes a terminal group, wherein theterminal group is selected from the group consisting of OR^(A) ₂,—SR^(A) ₂, —N—NR^(A) ₂, O—NR^(A) ₂, or NR^(A) ₂. At each occurrence, thevariable R² is independently selected from —H or

The wavy line labeled 2 can indicate a point of attachment to thestabilizing group.

In some embodiments, the linker includes polyethylenimine.

The crosslinker can include an epoxide functional group. In someembodiments, the crosslinker is a bis-epoxide. The bis-epoxide can be adiglycidyl ether. The diglycidyl ether can be selected from the groupconsisting of a 1,4-butanediol diglycidyl ether, a poly(ethylene glycol)diglycidyl ether, a neopentyl glycol diglycidyl ether, a glyceroldiglycidyl ether, a 1,4-Cyclohexanedimethanol diglycidyl ether, aresorcinol diglycidyl ether, a poly(propylene glycol) diglycidyl ether,a bisphenol A diglycidyl ether, diglycidyl ether (C₆H₁₀O₃), a1,2-propanediol diglycidyl ether, 1,4-butanediyl diglycidyl ether, andcombinations thereof. In some embodiments, the diglycidyl ether includesa 1,4-Butanediol diglycidyl ether.

The stabilizing group can include one or more of a —OH, —CO₂H, —CO₂CH₃,a phosphate, or a sulfate. For example, the stabilizing group caninclude a functional group selected from the group consisting of:

and combinations thereof.

The nanoparticle can be selected from the group consisting of a silicananoparticle, a polymeric nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andmixtures thereof. In some embodiments, the nanoparticle is a polystyrenenanoparticle. The polystyrene nanoparticle can be a derivatizedpolystyrene nanoparticle. The derivatized polystyrene nanoparticle canbe a sodium dodecyl sulfate derivitized polystyrene nanoparticle. Insome embodiments, the nanoparticle includes a metal oxide. In someembodiments, the nanoparticle includes a superparamagnetic metal oxide.The nanoparticle can include a metal oxide selected from the groupconsisting of an iron oxide, a nickel oxide, a cobalt oxide, amagnetite, a ferrite, and combinations thereof. The nanoparticle caninclude a metal oxide including an atom selected from the groupconsisting of Zn, Cr, Co, Dy, Er, Eu, Gd, Gd, Pr, Nd, In, Pr, Sm, Tb,Tm, and combinations thereof.

In some embodiments, the coating is electrostatically adsorbed on thenanoparticle.

In some embodiments, the crosslinked-coated nanoparticles, when at aconcentration of about 1,000 ppm in synthetic sea water, have ahydrodynamic radius of less than 30 nm after heating at 90° C. in thesynthetic sea water for 14 days.

Also provided herein is a crosslinked-coated nanoparticle composition.The composition includes an ion and a crosslinked-coated nanoparticle.The crosslinked-coated nanoparticle includes a nanoparticle and acoating. The coating includes a linker, a crosslinker, and a stabilizinggroup.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the coating is non-covalently bound to thenanoparticle. For example, the coating can be electrostatically adsorbedon the nanoparticle.

The linker can be crosslinked with the crosslinker. The stabilizinggroup can be covalently bound to the linker. In some embodiments, thelinker is crosslinked with the crosslinker and the linker is covalentlybound to the stabilizing group.

In some embodiments, the linker includes the subunit:

At each occurrence, the variable R¹ cab be selected from the from thegroup consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canbe a (C₁-C₁₀)alkyl interrupted with 0, 1, 2, 3, or 4 oxygen atoms orsubstituted or unsubstituted nitrogen atoms.

The linker can include a terminal group that is selected from groupconsisting of OR^(A) ₂, —SR^(A) ₂, —N—NR^(A) ₂, O—NR^(A) ₂, and NR^(A)₂. The variable R², at each occurrence, can be independently selectedfrom —H or

The wavy line labeled 2 can indicate a point of attachment to thestabilizing group.

In some embodiments, the linker includes polyethylenimine.

The crosslinker can include an epoxide functional group. For example,the crosslinker can be a bis-epoxide. In some embodiments, thebis-epoxide is a diglycidyl ether. The diglycidyl ether can be selectedfrom the group consisting of a 1,4-butanediol diglycidyl ether, apoly(ethylene glycol) diglycidyl ether, a neopentyl glycol diglycidylether, a glycerol diglycidyl ether, a 1,4-Cyclohexanedimethanoldiglycidyl ether, a resorcinol diglycidyl ether, a poly(propyleneglycol) diglycidyl ether, a bisphenol A diglycidyl ether, diglycidylether (C₆H₁₀O₃), a 1,2-propanediol diglycidyl ether, 1,4-butanediyldiglycidyl ether, and combinations thereof. In some embodiments, thediglycidyl ether includes a 1,4-Butanediol diglycidyl ether.

The stabilizing group can include one or more of the followingfunctional groups a —OH, —CO₂H, —CO₂CH₃, a phosphate, or a sulfate. Insome embodiments, the stabilizing group includes a functional groupselected from the group consisting of:

and combinations thereof.

The nanoparticle can be selected from the group consisting of a silicananoparticle, a polymeric nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andcombinations thereof. In some embodiments, the nanoparticle is apolystyrene nanoparticle. The nanoparticle can also be a derivatizedpolystyrene nanoparticle. For example, the nanoparticle can be a sodiumdodecyl sulfate derivatized polystyrene nanoparticle.

In some embodiments, the nanoparticle includes a metal oxide. Forexample, the nanoparticle can include a metal oxide selected from thegroup consisting of an iron oxide, a nickel oxide, a cobalt oxide, amagnetite, a ferrite, and combinations thereof. The nanoparticle caninclude a metal oxide including an atom selected from the groupconsisting of Zn, Cr, Co, Dy, Er, Eu, Gd, Gd, Pr, Nd, In, Pr, Sm, Tb,Tm, and combinations thereof. In some embodiments, the nanoparticleincludes a superparamagnetic metal oxide.

Also provided herein is a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a crosslinked-coatednanoparticle comprising a nanoparticle and a coating, The coatingincludes a linker, a crosslinker, and a stabilizing group.

In some embodiments, the coating is non-covalently bound to thenanoparticle. For example, the coating can be electrostatically adsorbedon the nanoparticle.

The linker can be crosslinked with the crosslinker. The stabilizinggroup can be covalently bound to the linker. In some embodiments, thelinker is crosslinked with the crosslinker and the linker is covalentlybound to the stabilizing group.

In some embodiments, the linker includes the subunit:

At each occurrence, the variable R¹ cab be selected from the from thegroup consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canbe a (C₁-C₁₀)alkyl interrupted with 0, 1, 2, 3, or 4 oxygen atoms orsubstituted or unsubstituted nitrogen atoms.

The linker can include a terminal group that is selected from groupconsisting of OR^(A) ₂, —SR^(A) ₂, —N—NR^(A) ₂, O—NR^(A) ₂, and NR^(A)₂. The variable R², at each occurrence, can be independently selectedfrom —H or

The wavy line labeled 2 can indicate a point of attachment to thestabilizing group.

In some embodiments, the linker includes polyethylenimine.

The crosslinker can include an epoxide functional group. For example,the crosslinker can be a bis-epoxide. In some embodiments, thebis-epoxide is a diglycidyl ether. The diglycidyl ether can be selectedfrom the group consisting of a 1,4-butanediol diglycidyl ether, apoly(ethylene glycol) diglycidyl ether, a neopentyl glycol diglycidylether, a glycerol diglycidyl ether, a 1,4-Cyclohexanedimethanoldiglycidyl ether, a resorcinol diglycidyl ether, a poly(propyleneglycol) diglycidyl ether, a bisphenol A diglycidyl ether, diglycidylether (C₆H₁₀O₃), a 1,2-propanediol diglycidyl ether, 1,4-butanediyldiglycidyl ether, and combinations thereof. In some embodiments, thediglycidyl ether includes a 1,4-Butanediol diglycidyl ether.

The stabilizing group can include one or more of the followingfunctional groups a —OH, —CO₂H, —CO₂CH₃, a phosphate, or a sulfate. Insome embodiments, the stabilizing group includes a functional groupselected from the group consisting of:

and combinations thereof.

The nanoparticle can be selected from the group consisting of a silicananoparticle, a polymeric nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andcombinations thereof. In some embodiments, the nanoparticle is apolystyrene nanoparticle. The nanoparticle can also be a derivatizedpolystyrene nanoparticle. For example, the nanoparticle can be a sodiumdodecyl sulfate derivatized polystyrene nanoparticle.

In some embodiments, the nanoparticle includes a metal oxide. Forexample, the nanoparticle can include a metal oxide selected from thegroup consisting of an iron oxide, a nickel oxide, a cobalt oxide, amagnetite, a ferrite, and combinations thereof. The nanoparticle caninclude a metal oxide including an atom selected from the groupconsisting of Zn, Cr, Co, Dy, Er, Eu, Gd, Gd, Pr, Nd, In, Pr, Sm, Tb,Tm, and combinations thereof. In some embodiments, the nanoparticleincludes a superparamagnetic metal oxide.

DESCRIPTION OF DRAWINGS

FIG. 1 shows a representative scanning electron micrographs of 45 nm PEI(polyethylenimine) coated silica nanoparticles, as provided in thisdisclosure.

FIG. 2 shows a schematic of nanoparticle surface chemistry (a) after PEIcoating and (b) glycidol modification, as provided in this disclosure.

FIG. 3 shows hydrodynamic size measurements of neat, PEI-coated, andPEI-glycidylated nanoparticles indicated small increments in size witheach surface modification step, as provided in this disclosure.

FIG. 4 shows a comparison of colloidal stability of the nanoparticles inArab-D brine at 90° C. for 8 days showing that (a) the glycidylatednanoparticles remain stable over the testing period and (b) thePEI-coated nanoparticles have grown in size (aggregation), as providedin this disclosure.

FIG. 5 shows absorbance maximum at 550 nm of tetramethylrhodamine after8 days in Arab-D brine interfaced with finely crushed carbonatereservoir rocks.

FIG. 6 shows glycidylated PEI nanoparticles after 21 days at 90° C.

FIG. 7 shows the dynamic light scattering for glycidylated PEI-coatednanoparticles in seawater after 8 days at 90° C.

FIG. 8 shows the dynamic light scattering for glycidylated PEI-coatednanoparticle compositions doped with calcium ions in seawater after 8days at 90° C.

FIG. 9 shows coating, crosslinking, and glycidylation of sodium dodecylsulfate (SDS) derivatized polystyrenic nanoparticles.

FIG. 10 shows the dynamic light scattering for glycidylatedcrosslinked-PEI coated nanoparticle compositions in low salinity Arab-Dbrine, synthetic sea water, and synthetic seawater doped with calciumover a period of 14 days at 90° C.

DETAILED DESCRIPTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part inthe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (for example, 1%, 2%, 3%, and 4%) and the sub-ranges(for example, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within theindicated range. The statement “about X to Y” has the same meaning as“about X to about Y,” unless indicated otherwise. Likewise, thestatement “about X, Y, or about Z” has the same meaning as “about X,about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” has the same meaning as “A, B,or A and B.” In addition, it is to be understood that the phraseology orterminology employed in this disclosure, and not otherwise defined, isfor the purpose of description only and not of limitation. Any use ofsection headings is intended to aid reading of the document and is notto be interpreted as limiting; information that is relevant to a sectionheading may occur within or outside of that particular section. Allpublications, patents, and patent documents referred to in this documentare incorporated by reference in this disclosure in their entirety, asthough individually incorporated by reference. In the event ofinconsistent usages between this document and those documents soincorporated by reference, the usage in the incorporated referenceshould be considered supplementary to that of this document; forirreconcilable inconsistencies, the usage in this document controls.

In the methods of manufacturing described in this disclosure, the actscan be carried out in any order, except when a temporal or operationalsequence is explicitly recited. Furthermore, specified acts can becarried out concurrently unless explicit claim language recites thatthey be carried out separately. For example, a claimed act of doing Xand a claimed act of doing Y can be conducted simultaneously within asingle operation, and the resulting process will fall within the literalscope of the claimed process.

The term “about” as used in this disclosure can allow for a degree ofvariability in a value or range, for example, within 10%, within 5%, orwithin 1% of a stated value or of a stated limit of a range.

The term “substantially” as used in this disclosure refers to a majorityof, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%,97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used in this disclosure refers to but is notlimited to any carbon-containing functional group. For example, anoxygen-containing group such as an alkoxy group, aryloxy group,aralkyloxy group, oxo(carbonyl) group, a carboxyl group including acarboxylic acid, carboxylate, and a carboxylate ester; asulfur-containing group such as an alkyl and aryl sulfide group; andother heteroatom-containing groups. Non-limiting examples of organicgroups include OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃, R, C(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂,OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂,N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂,N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, in which R canbe hydrogen (in examples that include other carbon atoms) or acarbon-based moiety, and in which the carbon-based moiety can itself befurther substituted.

The term “substituted” as used in this disclosure refers to an organicgroup as defined in this disclosure or molecule in which one or morehydrogen atoms contained therein are replaced by one or morenon-hydrogen atoms. The term “functional group” or “substituent” as usedin this disclosure refers to a group that can be or is substituted ontoa molecule or onto an organic group. Examples of substituents orfunctional groups include, but are not limited to, a halogen (forexample, F, Cl, Br, and I); an oxygen atom in groups such as hydroxygroups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl)groups, carboxyl groups including carboxylic acids, carboxylates, andcarboxylate esters; a sulfur atom in groups such as thiol groups, alkyland aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonylgroups, and sulfonamide groups; a nitrogen atom in groups such asamines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides,azides, and enamines; and other heteroatoms in various other groups.

The term “alkyl” as used in this disclosure refers to straight chain andbranched alkyl groups and cycloalkyl groups having from 1 to 40 carbonatoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in someembodiments, from 1 to 8 carbon atoms. Examples of straight chain alkylgroups include those with from 1 to 8 carbon atoms such as methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octylgroups. Examples of branched alkyl groups include, but are not limitedto, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used in this disclosure, the term “alkyl”encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as otherbranched chain forms of alkyl. Representative substituted alkyl groupscan be substituted one or more times with any of the groups listed inthis disclosure, for example, amino, hydroxy, cyano, carboxy, nitro,thio, alkoxy, and halogen groups.

The term “alkenyl” as used in this disclosure refers to straight andbranched chain and cyclic alkyl groups as defined in this disclosure,except that at least one double bond exists between two carbon atoms.Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20carbon atoms, or 2 to 12 carbons or, in some embodiments, from 2 to 8carbon atoms. Examples include, but are not limited to vinyl,—CH═CH(CH₃), —CH═C(CH₃)₂, —C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂,cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl,and hexadienyl among others.

The term “alkynyl” as used in this disclosure refers to straight andbranched chain alkyl groups, except that at least one triple bond existsbetween two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbonatoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in someembodiments, from 2 to 8 carbon atoms. Examples include, but are notlimited to —C═CH, —C═C(CH₃), —C═C(CH₂CH₃), —CH₂C═CH, —CH₂C═C(CH₃), and—CH₂C═C(CH₂CH₃) among others.

The term “acyl” as used in this disclosure refers to a group containinga carbonyl moiety in which the group is bonded via the carbonyl carbonatom. The carbonyl carbon atom is also bonded to another carbon atom,which can be part of an alkyl, aryl, aralkyl cycloalkyl,cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl,heteroarylalkyl group or the like. In the special case in which thecarbonyl carbon atom is bonded to a hydrogen, the group is a “formyl”group, an acyl group as the term is defined in this disclosure. An acylgroup can include 0 to about 12-20 or 12-40 additional carbon atomsbonded to the carbonyl group. An acyl group can include double or triplebonds within the meaning in this disclosure. An acryloyl group is anexample of an acyl group. An acyl group can also include heteroatomswithin the meaning here. A nicotinoyl group (pyridyl-3-carbonyl) is anexample of an acyl group within the meaning in this disclosure. Otherexamples include acetyl, benzoyl, phenylacetyl, pyridylacetyl,cinnamoyl, and acryloyl groups and the like. When the group containingthe carbon atom that is bonded to the carbonyl carbon atom contains ahalogen, the group is termed a “haloacyl” group. An example is atrifluoroacetyl group.

The term “cycloalkyl” as used in this disclosure refers to cyclic alkylgroups such as, but not limited to, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In someembodiments, the cycloalkyl group can have 3 to about 8-12 ring members,whereas in other embodiments the number of ring carbon atoms range from3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycycliccycloalkyl groups such as, but not limited to, norbornyl, adamantyl,bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused ringssuch as, but not limited to, decalinyl, and the like. Cycloalkyl groupsalso include rings that are substituted with straight or branched chainalkyl groups as defined in this disclosure. Representative substitutedcycloalkyl groups can be mono-substituted or substituted more than once,such as, but not limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstitutedcyclohexyl groups or mono-, di- or tri-substituted norbornyl orcycloheptyl groups, which can be substituted with, for example, amino,hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. Theterm “cycloalkenyl” alone or in combination denotes a cyclic alkenylgroup.

The term “aryl” as used in this disclosure refers to cyclic aromatichydrocarbons that do not contain heteroatoms in the ring. Thus arylgroups include, but are not limited to, phenyl, azulenyl, heptalenyl,biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined in this disclosure. Representative substitutedaryl groups can be mono-substituted or substituted more than once, suchas, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8substituted naphthyl groups, which can be substituted with carbon ornon-carbon groups such as those listed in this disclosure.

The term “aralkyl” as used in this disclosure refers to alkyl groups asdefined in this disclosure in which a hydrogen or carbon bond of analkyl group is replaced with a bond to an aryl group as defined in thisdisclosure. Representative aralkyl groups include benzyl and phenylethylgroups and fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl.Aralkenyl groups are alkenyl groups as defined in this disclosure inwhich a hydrogen or carbon bond of an alkyl group is replaced with abond to an aryl group as defined in this disclosure.

The term “heterocyclyl” as used in this disclosure refers to aromaticand non-aromatic ring compounds containing three or more ring members,of which one or more is a heteroatom such as, but not limited to, N, O,and S. Thus, a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl,or if polycyclic, any combination thereof. In some embodiments,heterocyclyl groups include 3 to about 20 ring members, whereas othersuch groups have 3 to about 15 ring members. A heterocyclyl groupdesignated as a C2-heterocyclyl can be a 5-ring with two carbon atomsand three heteroatoms, a 6-ring with two carbon atoms and fourheteroatoms and so forth. Likewise a C4-heterocyclyl can be a 5-ringwith one heteroatom, a 6-ring with two heteroatoms, and so forth. Thenumber of carbon atoms plus the number of heteroatoms equals the totalnumber of ring atoms. A heterocyclyl ring can also include one or moredouble bonds. A heteroaryl ring is an embodiment of a heterocyclylgroup. The phrase “heterocyclyl group” includes fused ring speciesincluding those that include fused aromatic and non-aromatic groups.

The term “heterocyclylalkyl” as used in this disclosure refers to alkylgroups as defined in this disclosure in which a hydrogen or carbon bondof an alkyl group as defined in this disclosure is replaced with a bondto a heterocyclyl group as defined in this disclosure. Representativeheterocyclyl alkyl groups include, but are not limited to, furan-2-ylmethyl, furan -3-yl methyl, pyridine-3-yl methyl, tetrahydrofuran-2-ylethyl, and indol-2-yl propyl.

The term “heteroarylalkyl” as used in this disclosure refers to alkylgroups as defined in this disclosure in which a hydrogen or carbon bondof an alkyl group is replaced with a bond to a heteroaryl group asdefined in this disclosure.

The term “alkoxy” as used in this disclosure refers to an oxygen atomconnected to an alkyl group, including a cycloalkyl group, as aredefined in this disclosure. Examples of linear alkoxy groups include butare not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy,hexyloxy, and the like. Examples of branched alkoxy include but are notlimited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy,isohexyloxy, and the like. Examples of cyclic alkoxy include but are notlimited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,and the like. An alkoxy group can include one to about 12-20 or about12-40 carbon atoms bonded to the oxygen atom, and can further includedouble or triple bonds, and can also include heteroatoms. For example,an allyloxy group is an alkoxy group within the meaning in thisdisclosure. A methoxyethoxy group is also an alkoxy group within themeaning in this disclosure, as is a methylenedioxy group in a contextwhere two adjacent atoms of a structure are substituted therewith.

The term “amine” as used in this disclosure refers to primary,secondary, and tertiary amines having, for example, the formulaN(group)₃ in which each group can independently be H or non-H, such asalkyl, aryl, and the like. Amines include but are not limited to R—NH₂,for example, alkylamines, arylamines, alkylarylamines; R₂NH in whicheach R is independently selected, such as dialkylamines, diarylamines,aralkylamines, heterocyclylamines and the like; and R₃N in which each Ris independently selected, such as trialkylamines, dialkylarylamines,alkyldiarylamines, triarylamines, and the like. The term “amine” alsoincludes ammonium ions as used in this disclosure.

The term “amino group” as used in this disclosure refers to asubstituent of the form —NH₂, —NHR, —NR₂, —NR₃ ⁺, in which each R isindependently selected, and protonated forms of each, except for —NR₃ ⁺,which cannot be protonated. Accordingly, any compound substituted withan amino group can be viewed as an amine. An “amino group” within themeaning in this disclosure can be a primary, secondary, tertiary, orquaternary amino group. An “alkylamino” group includes a monoalkylamino,dialkylamino, and trialkylamino group.

The terms “halo,” “halogen,” or “halide” group, as used in thisdisclosure, by themselves or as part of another substituent, mean,unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

The term “haloalkyl” group, as used in this disclosure, includesmono-halo alkyl groups, poly-halo alkyl groups in which all halo atomscan be the same or different, and per-halo alkyl groups, in which allhydrogen atoms are replaced by halogen atoms, such as fluoro. Examplesof haloalkyl include trifluoromethyl, 1,1-dichloroethyl,1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, andthe like.

The term “hydrocarbon” as used in this disclosure refers to a functionalgroup or molecule that includes carbon and hydrogen atoms. The term canalso refer to a functional group or molecule that normally includes bothcarbon and hydrogen atoms but in which all the hydrogen atoms aresubstituted with other functional groups.

As used in this disclosure, the term “hydrocarbyl” refers to afunctional group derived from a straight chain, branched, or cyclichydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl,or any combination thereof.

The term “solvent” as used in this disclosure refers to a liquid thatcan dissolve a solid, another liquid, or a gas to form a solution.Non-limiting examples of solvents are silicones, organic compounds,water, alcohols, ionic liquids, and supercritical fluids.

The term “room temperature” as used in this disclosure refers to atemperature of about 15° C. to about 28° C.

The term “standard temperature and pressure” as used in this disclosurerefers to 20° C. and 101 kPa.

As used in this disclosure, “degree of polymerization” is the number ofrepeating units in a polymer.

As used in this disclosure, the term “polymer” refers to a moleculehaving at least one repeating unit and can include copolymers.

The term “copolymer” as used in this disclosure refers to a polymer thatincludes at least two different repeating units. A copolymer can includeany suitable number of repeating units.

The term “downhole” as used in this disclosure refers to under thesurface of the earth, such as a location within or fluidly connected toa wellbore.

As used in this disclosure, the term “drilling fluid” refers to fluids,slurries, or muds used in drilling operations downhole, such as duringthe formation of the wellbore.

As used in this disclosure, the term “stimulation fluid” refers tofluids or slurries used downhole during stimulation activities of thewell that can increase the production of a well, including perforationactivities. In some examples, a stimulation fluid can include afracturing fluid or an acidizing fluid.

As used in this disclosure, the term “clean-up fluid” refers to fluidsor slurries used downhole during clean-up activities of the well, suchas any treatment to remove material obstructing the flow of desiredmaterial from the subterranean formation. In one example, a clean-upfluid can be an acidification treatment to remove material formed by oneor more perforation treatments. In another example, a clean-up fluid canbe used to remove a filter cake.

As used in this disclosure, the term “fracturing fluid” refers to fluidsor slurries used downhole during fracturing operations.

As used in this disclosure, the term “spotting fluid” refers to fluidsor slurries used downhole during spotting operations, and can be anyfluid designed for localized treatment of a downhole region. In oneexample, a spotting fluid can include a lost circulation material fortreatment of a specific section of the wellbore, such as to seal offfractures in the wellbore and prevent sag. In another example, aspotting fluid can include a water control material. In some examples, aspotting fluid can be designed to free a stuck piece of drilling orextraction equipment, can reduce torque and drag with drillinglubricants, prevent differential sticking, promote wellbore stability,and can help to control mud weight.

As used in this disclosure, the term “completion fluid” refers to fluidsor slurries used downhole during the completion phase of a well,including cementing compositions.

As used in this disclosure, the term “remedial treatment fluid” refersto fluids or slurries used downhole for remedial treatment of a well.Remedial treatments can include treatments designed to increase ormaintain the production rate of a well, such as stimulation or clean-uptreatments.

As used in this disclosure, the term “abandonment fluid” refers tofluids or slurries used downhole during or preceding the abandonmentphase of a well.

As used in this disclosure, the term “acidizing fluid” refers to fluidsor slurries used downhole during acidizing treatments. In one example,an acidizing fluid is used in a clean-up operation to remove materialobstructing the flow of desired material, such as material formed duringa perforation operation. In some examples, an acidizing fluid can beused for damage removal.

As used in this disclosure, the term “cementing fluid” refers to fluidsor slurries used during cementing operations of a well. For example, acementing fluid can include an aqueous mixture including at least one ofcement and cement kiln dust. In another example, a cementing fluid caninclude a curable resinous material such as a polymer that is in an atleast partially uncured state.

As used in this disclosure, the term “water control material” refers toa solid or liquid material that interacts with aqueous materialdownhole, such that hydrophobic material can more easily travel to thesurface and such that hydrophilic material (including water) can lesseasily travel to the surface. A water control material can be used totreat a well to cause the proportion of water produced to decrease andto cause the proportion of hydrocarbons produced to increase, such as byselectively binding together material between water-producingsubterranean formations and the wellbore while still allowinghydrocarbon-producing formations to maintain output.

As used in this disclosure, the term “packer fluid” refers to fluids orslurries that can be placed in the annular region of a well betweentubing and outer casing above a packer. In various examples, the packerfluid can provide hydrostatic pressure in order to lower differentialpressure across the sealing element, lower differential pressure on thewellbore and casing to prevent collapse, and protect metals andelastomers from corrosion.

As used in this disclosure, the term “fluid” refers to liquids and gels,unless otherwise indicated.

As used in this disclosure, the term “subterranean material” or“subterranean formation” refers to any material under the surface of theearth, including under the surface of the bottom of the ocean. Forexample, a subterranean formation or material can be any section of awellbore and any section of a subterranean petroleum- or water-producingformation or region in fluid contact with the wellbore. Placing amaterial in a subterranean formation can include contacting the materialwith any section of a wellbore or with any subterranean region in fluidcontact therewith. Subterranean materials can include any materialsplaced into the wellbore such as cement, drill shafts, liners, tubing,casing, or screens; placing a material in a subterranean formation caninclude contacting with such subterranean materials. In some examples, asubterranean formation or material can be any below-ground region thatcan produce liquid or gaseous petroleum materials, water, or any sectionbelow-ground in fluid contact therewith. For example, a subterraneanformation or material can be at least one of an area desired to befractured, a fracture or an area surrounding a fracture, and a flowpathway or an area surrounding a flow pathway, in which a fracture or aflow pathway can be optionally fluidly connected to a subterraneanpetroleum- or water-producing region, directly or through one or morefractures or flow pathways.

As used in this disclosure, “treatment of a subterranean formation” caninclude any activity directed to extraction of water or petroleummaterials from a subterranean petroleum- or water-producing formation orregion, for example, including drilling, stimulation, hydraulicfracturing, clean-up, acidizing, completion, cementing, remedialtreatment, abandonment, and the like.

As used in this disclosure, a “flow pathway” downhole can include anysuitable subterranean flow pathway through which two subterraneanlocations are in fluid connection. The flow pathway can be sufficientfor petroleum or water to flow from one subterranean location to thewellbore or vice-versa. A flow pathway can include at least one of ahydraulic fracture, and a fluid connection across a screen, acrossgravel pack, across proppant, including across resin-bonded proppant orproppant deposited in a fracture, and across sand. A flow pathway caninclude a natural subterranean passageway through which fluids can flow.In some embodiments, a flow pathway can be a water source and caninclude water. In some embodiments, a flow pathway can be a petroleumsource and can include petroleum. In some embodiments, a flow pathwaycan be sufficient to divert from a wellbore, fracture, or flow pathwayconnected thereto at least one of water, a downhole fluid, or a producedhydrocarbon.

As used in this disclosure, a “carrier fluid” refers to any suitablefluid for suspending, dissolving, mixing, or emulsifying with one ormore materials to form a composition. For example, the carrier fluid canbe at least one of crude oil, dipropylene glycol methyl ether,dipropylene glycol dimethyl ether, dipropylene glycol methyl ether,dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycolmethyl ether, ethylene glycol butyl ether, diethylene glycol butylether, butylglycidyl ether, propylene carbonate, D-limonene, a C2-C40fatty acid C1-C10 alkyl ester (for example, a fatty acid methyl ester),tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethylsulfoxide, dimethyl formamide, a petroleum distillation product offraction (for example, diesel, kerosene, napthas, and the like) mineraloil, a hydrocarbon oil, a hydrocarbon including an aromaticcarbon-carbon bond (for example, benzene, toluene), a hydrocarbonincluding an alpha olefin, xylenes, an ionic liquid, methyl ethylketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol,propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), analiphatic hydrocarbon (for example, cyclohexanone, hexane), water,brine, produced water, flowback water, brackish water, and sea water.The fluid can form about 0.001 wt % to about 99.999 wt % of acomposition, or a mixture including the same, or about 0.001 wt % orless, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99,or about 99.999 wt % or more

Methods of Treating a Subterranean Formation with Coated NanoparticleCompositions.

Provided in this disclosure is a method of treating a subterraneanformation. The method includes placing in a subterranean formation acomposition including a coated nanoparticle and an ion. The coatednanoparticle includes a nanoparticle, a linker, and a stabilizing group.The linker includes an anchoring group, a spacer, and a terminal group.Further, the anchoring group is covalently bound to the nanoparticle andat least one of the terminal groups is covalently bound to at least onestabilizing group.

In some embodiments, the composition further includes an aqueous liquid.The aqueous liquid can include at least one of water, brine, producedwater, flowback water, bracking water, Arab-D-brine, fresh water,mineral waters, sea water, and other waters of varying salinity andmineral concentration. The aqueous liquid can include at least one of adrilling fluid, a fracturing fluid, a diverting fluid, and a lostcirculation treatment fluid.

In some embodiments, method further includes obtaining or providing thecomposition, in which the obtaining or providing of the compositionoccurs above-surface. In some embodiments, the method further includesobtaining or providing the composition, in which the obtaining orproviding of the composition occurs in the subterranean formation. Forexample, the composition can be provided or obtained in the subterraneanformation by providing the coated nanoparticles from one source andprior to, during, or after providing the coated nanoparticles, the ioncan be provided from a separate source. For example, the ion could beinitially provided in the subterranean formation in an aqueous liquidand, subsequently, the coated nanoparticles could be provided to provideor obtain the composition.

In some embodiments, the method is at least one of a method of drillingthe subterranean formation, a method of fracturing the subterraneanformation, a method of conformance control, a method of subsurfaceimaging the subterranean formation, a method of aquifer remediation inthe subterranean formation.

In some embodiments, the coated nanoparticles have a lower criticalsolution temperature (“LCST”) of greater than about 90° C., 100° C.,110° C. or greater than about 120° C. For example, the coatednanoparticles can have an LCST of greater than about 90° C.

In some embodiments, the coated nanoparticles have a hydrodynamic radiusof less than about 100 nm. For example, as determined by dynamic lightscattering, the coated nanoparticles of the composition can have ahydrodynamic radius of less than about 100 nm in synthetic sea water orsynthetic Arab-D brine at room temperature. For example, as determinedby dynamic light scattering, the coated nanoparticles of the compositioncan have a hydrodynamic radius of less than about 100 nm, 90 nm, 80 nm,70 nm, 60 nm, 50 nm or less than about 40 nm in sea water or Arab-Dbrine in room temperature.

In some embodiments, the coated nanoparticles, when at a concentrationof about 500 ppm, 1,000 ppm, 1,500 ppm, 2,000 ppm, 3,000 ppm, or about4,000 ppm in synthetic sea water, have a hydrodynamic radius of lessthan about 250 nm after heating at 90° C. in the synthetic sea for 8days, as measured by dynamic light scattering. In some embodiments, thecoated nanoparticles, when at a concentration of about 2,000 ppm insynthetic sea water, have a hydrodynamic radius of less than about 250nm after heating at 90° C. in the synthetic sea water for 8 days, asmeasured by dynamic light scattering. In some embodiments, the coatednanoparticles, when at a concentration of about 1,000 ppm in syntheticsea water, have a hydrodynamic radius of less than about 250 nm afterheating at 90° C. in the synthetic sea water for 8 days, as measured bydynamic light scattering. In some embodiments, the coated nanoparticles,when at a concentration of about 500 ppm, 1,000 ppm, 1,500 ppm, 2,000ppm, 3,000 ppm, or about 4,000 ppm in synthetic Arab-D brine, have ahydrodynamic radius of less than about 250 nm after heating at 90° C. inthe synthetic Arab-D brine for 8 days, as measured by dynamic lightscattering. Synthetic sea water and synthetic Arab-D brine are describedin Table 1. In some embodiments, the coated nanoparticles, when at aconcentration of about 2,000 ppm in synthetic Arab-D brine have ahydrodynamic radius of less than about 250 nm after heating at 90° C. inthe synthetic Arab-D brine for 8 days, as measured by dynamic lightscattering. In some embodiments, the coated nanoparticles, when at aconcentration of about 1,000 ppm in synthetic Arab-D brine have ahydrodynamic radius of less than about 250 nm after heating at 90° C. inthe synthetic Arab-D brine for 8 days, as measured by dynamic lightscattering. Synthetic sea water and synthetic Arab-D brine are describedin Table 1.

Synthetic Seawater Synthetic Arab-D (mol/L) Brine (mol/L) NaCl 0.70221.2764 CaCl₂•2H₂O 0.0162 0.3387 MgCl₂•6H₂O 0.0868 0.0648 BaCl₂ 0.000.0001 Na₂SO₄ 0.0447 0.0042 NaHCO₃ 0.0020 0.00607 Na₂CO₃ 0.00 0.00

In some embodiments, the coated nanoparticles have a hydrodynamic radiusthat is less than the hydrodynamic radius of similar nanoparticleswithout the one or more stabilizing groups in a similar compositionunder similar conditions. For example, the coated nanoparticles can havea hydrodynamic radius that is less than the hydrodynamic radius ofsimilar nanoparticles without the one or more stabilizing groups in asimilar composition in water, brine, produced water, flowback water,bracking water, Arab-D-brine, fresh water, mineral waters, sea water ormixtures thereof.

In some embodiments, the nanoparticle is selected from the groupconsisting of a silica nanoparticle, a metal oxide nanoparticle, asuperparamagnetic nanoparticle, an upconverting nanoparticle (e.g., rareearth upconverting nanoparticles), polymer-based nanoparticles such aspolystyrene based nanoparticles, carbonaceous nanoparticles such ascarbon black, carbon nanotubes, graphene, graphene platelets, andmixtures thereof. In some embodiments, the nanoparticle can include ametal oxide. In some embodiments, the nanoparticle includes an ironoxide, a nickel oxide, a cobalt oxide, a magnetite, a ferrite, orcombinations thereof. In some embodiments, the nanoparticle is asuperparamagnetic nanoparticle. Examples of superparamagneticnanoparticles include iron oxides, such as Fe₃O₄ and γ-Fe₂O₃, puremetals, such as Fe and Co, spinel-type ferromagnets, such as MgFe₂O₄,MnFe₂O₄, and CoFe₂O₄, as well as alloys, such as CoPt₃ and FePt. In someembodiments, the nanoparticle includes a fluoride. For example, thenanoparticle can include upconverting rare earth nanoparticles such asdoped YF4 nanoparticles. In some embodiments, the nanoparticle includesa metal oxide including an atom selected from the group consisting ofZn, Cr, Co, Dy, Er, Eu, Fe, Gd, Gd, Pr, Nd, Ni, In, Pr, Sm, Tb, Tm, andcombinations thereof.

In some embodiments, the nanoparticle is a silica nanoparticle. Forexample, the nanoparticle can be a fluorescent silica nanoparticle.

When the composition includes a coated superparamagnetic nanoparticlethe coated superparamagnetic nanoparticles can be used as contrastagents for electromagnetic imaging of subsurface formations. As used inthis disclosure, the term “superparamagnetic nanoparticle” refers to ananoparticle that exhibits strong paramagnetic behavior in the presenceof an applied magnetic field. In some embodiments, the superparamagneticnanoparticles can include iron oxides, such as Fe₃O₄ and γ-Fe₂O₃, puremetals, such as Fe and Co, spinel-type ferromagnets, such as MgFe₂O₄,MnFe₂O₄, and CoFe₂O₄, as well as alloys, such as CoPt₃ and FePt. Forexample, the nanoparticles can include a superparamagnetic iron oxidecores. Nanoparticles including a superparamagnetic core (for example,superparamagnetic nanoparticles) can exhibit strong paramagneticbehavior in the presence of an applied magnetic field. In the absence ofan applied field, superparamagnetic nanoparticles can exhibit nomagnetic moment. This is due to the nanometer length scale of themagnetic domains in the superparamagnetic nanoparticle. In someembodiments, these superparamagnetic nanoparticle can be used ascontrast agents for electromagnetic crosswell imaging. The change inmagnetic susceptibility of the composition including superparamagneticnanoparticles provides contrast against native fluids. Consequently, thecompositions described in this disclosure provides for an increase inmagnetic susceptibility without a loss in colloidal stability.

In some embodiments, the nanoparticles have an average particle size ofabout 10 nm to about 1,000 nm. For example, the nanoparticles can havean average size of about 10 to 100 nm, 20 to 90 nm, or about 30 to 80nm, as determined by scanning electron microscopy prior to forming thecoated nanoparticle. As used in this disclosure, the term “average size”refers to the arithmetic mean of the distribution of nanoparticle sizesin a plurality of nanoparticles.

The linker includes an anchoring group, a spacer, and a terminal group.

In some embodiments, the linker spacer and terminal group includes apolyamine (e.g., polyallylamine, chitosan, and polyethylenimine). Insome embodiments, the linker spacer and terminal group includespolyethylenimine. For example, the nanoparticle and covalently boundlinker can be obtained by reacting trimethoxysilylpropyl modifiedpolyethylenimine with the nanoparticle.

In some embodiments, the anchoring group is a silane that is covalentlybound to the nanoparticle.

In some embodiments, the linker spacer includes the subunit:

The variable R¹ can be selected from the from the group consisting of—H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 indicates a point of attachment to another linker on thecoated nanoparticle. The variable A can be a (C₁-C₁₀)alkyl interruptedwith 0, 1, 2, 3, or 4 oxygen atoms or substituted or unsubstitutednitrogen atoms. For example, A can be —CH₂CH₂—.

In some embodiments, the linker terminal group is —OR^(A), —SR^(A),—N—NR^(A) ₂, O—NR^(A) ₂, or NR^(A) ₂. The variable R^(A), at eachoccurrence can be independently selected from —H or

The wavy line labeled 2 indicates a point of attachment to thestabilizing group.

In some embodiments, the stabilizing group includes one or more of a—OH, —CO₂H, —CO₂CH₃, a phosphonate, a phosphate, a sulfonate, or asulfate. For example, the stabilizing group can include a functionalgroup selected from the group consisting of:

and combinations thereof. The wavy line indicates a point of attachmentto the linker terminal group.

In some embodiments, the stabilizing group can be a carbohydrate. Forexample, the stabilizing group include at least one of a monosaccharide,an oligosaccharide, or a polysaccharide. In some embodiments, thepolysaccharide is selected from the group consisting of alginate,chitosan, curdlan, dextran, derivatized dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, diutan, welan, starch, derivatized starch, tamarind,tragacanth, guar gum, derivatized guar gum (for example, hydroxypropylguar, carboxy methyl guar, or carboxymethyl hydroxypropyl guar), gumghatti, gum arabic, locust bean gum, cellulose, and derivatizedcellulose (for example, carboxymethyl cellulose, hydroxyethyl cellulose,carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, or methylhydroxy ethyl cellulose). For example, the polysaccharide can bedextran.

The polysaccharide can have an average molecular weight of about 1,000Daltons (Da) to about 150,000 Da. For example, the polysaccharide canhave an average molecular weight of about 10,000 Da to about 140,000 Da,about 30,000 Da to about 130,000 Da, 50,000 to about 120,000 Da, 70,000Da to about 110,000 Da, or about 80,000 Da to about 100,000 Da, or about1,000 Da, 5,000 Da, 10,000 Da, 20,000 Da, 30,000 Da, 40,000 Da, 50,000Da, 60,000 Da, 70,000 Da, 80,000 Da, 90,000 Da, 100,000 Da, 110,000 Da,120,000 Da, 130,000 Da, 140,000 Da, or about 150,000 Da or greater.

In some embodiments, the coated nanoparticles have a positive zetapotential.

In some embodiments, about 5% to about 95% of terminal groups arecovalently bound to a stabilizing group. In some embodiments, about 5%,10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%,80%, 85%, 90%, or about 95% of terminal groups are covalently bound to astabilizing group. For example, about 75% of terminal groups can becovalently bound to a stabilizing group.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the composition includes an aqueous liquid and anion. The ion can be present at a concentration of about 0.05 M to about2 M. For example, the ion can be present at a concentration of about0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1.0 M, 1.5 M, or about 2 M. In someembodiments, the ion can be present at a concentration of about 0.05 Mto about 0.3 M. For example, the ion can be present at a concentrationof about 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, or about0.3 M. In some embodiments, the ion can be present at a concentration ofabout 0.6 M to about 0.9 M. For example, the ion can be present at aconcentration of about 0.6 M, 0.7 M, 0.8 M, or about 0.9 M.

In some embodiments, the composition includes sea water and a calciumion where the calcium ion is present at a concentration at aconcentration of about 0.05 M to about 0.3 M. For example, the ion canbe present at a concentration of about 0.05 M, 0.06 M, 0.07 M, 0.08 M,0.09 M, 0.1 M, 0.2 M, or about 0.3 M.

The ions present in the composition can be closely associated with thestabilizing groups. For example, the ions present in the composition canbe bound to the stabilizing groups through non-covalent interactionssuch as through Van der Waals forces. Further, the ions present in thecomposition can be bound to the stabilizing groups through coordinatedbinding.

In some embodiments, the providing or obtaining the composition includesdetermining the presence and concentration of at least one ion of awater in a subterranean formation and doping the composition with thedetermined ion. For example, the composition can be doped with at leastone ion found in a water of a subterranean formation such that themolarity of the ion in the composition is at least 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, 80%, 85%, 90% or atleast 95% of the molarity of the ion found in the water of thesubterranean formation.

In some embodiments, the composition further includes a kosmotropic ion.In some embodiments, the method further includes aggregating andprecipitating the coated nanoparticles in the subterranean formation bythe addition of a kosmotropic ion, such as a sulfate, a phosphate, Mg²⁺,Li⁺, or any other suitable kosmotropic ion. In some embodiments, themethod is a method of fluid diversion and further includes aggregating,or aggregating and precipitating, the coated nanoparticles in thesubterranean formation by the addition of a kosmotropic ion. In someembodiments, the method is a method of conformance control and furtherincludes aggregating, or aggregating and precipitating, of the coatednanoparticles in the subterranean formation by the addition of akosmotropic ion. For example, after the composition has been placed inthe subterranean formation a kosmotropic ion may be added to thecomposition. Addition of the kosmotropic ion can lead to aggregation, oraggregation and precipitation, of the coated nanoparticles in thesubterranean formation. Such, compositions including kosmotropic ionsare useful in fluid diversion or conformance control.

As used in this disclosure, the term “kosmotropic ion” refers to ionsthat contribute to the stability and structure of water-waterinteractions. Kosmotropes typically cause water molecules to favorablyinteract, which also stabilizes intermolecular interactions inmacromolecules. Examples of ionic kosmotropic ions include sulfate,phosphate, Mg²⁺, Li⁺, and any other suitable substance. Based on freeenergy of hydration (ΔG_(hydro)) of the salts, an increasing negativeΔG_(hydro), results in a more kosmotropic the salt, for example. Othersuitable kosmotropes may include a sulfate, phosphate, hydrogenphosphatesalt, ammonium sulfate, sodium sulfate, citrates, oxalates, and anyother order increasing substance. The counterion may include Group IAmetal ions, Group IIA metal ions, ammonium ions, and other suitableions.

In some embodiments, the composition further includes a chaotropic ion,such as urea, guanidinium chloride, lithium perchlorate, or any othersuitable chaotropic ion. In some embodiments, the method furtherincludes aggregating the coated nanoparticles at an oil-water interface.For example, the coated nanoparticles can be aggregated at one or moreoil-water interfaces by the addition of a chaotropic ion, such as urea,guanidinium chloride, lithium perchlorate, and any other suitablechaotropic ion.

As used in this disclosure, the term “chaotripoc ion” refers to ionsthat disrupt the three dimensional structure of water. Chaotropestypically interfere with stabilizing intra-molecular interactionsmediated by non-covalent forces, such as hydrogen bonds, Van der Waalsforces, and hydrophobic effects. Examples of chaotropes include urea,guanidinium chloride, and lithium perchlorate.

In some embodiments, the composition further includes a counterion. Forexample, the counterion can be a halide, such as fluoro, chloro, iodo,or bromo. In other examples, the counterion can be nitrate, hydrogensulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate,iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide,amide, cyanate, hydroxide, permanganate. The counterion can be aconjugate base of any carboxylic acid, such as acetate or formate.

In some embodiments, the method further includes combining thecomposition with an aqueous or oil-based fluid including a drillingfluid, a stimulation fluid, a fracturing fluid, a spotting fluid, aclean-up fluid, a completion fluid, a remedial treatment fluid, anabandonment fluid, a pill, an acidizing fluid, a cementing fluid, apacker fluid, a imaging fluid or a combination thereof, to form amixture, in which the placing the composition in the subterraneanformation includes placing the mixture in the subterranean formation.When the composition is combined with an oil-based fluid, thecomposition can form emulsions.

In some embodiments, at least one of prior to, during, and after theplacing of the composition in the subterranean formation, thecomposition is used in the subterranean formation, at least one of aloneand in combination with other materials, as a drilling fluid, astimulation fluid, a fracturing fluid, a spotting fluid, a clean-upfluid, a completion fluid, a remedial treatment fluid, an abandonmentfluid, a pill, an acidizing fluid, a cementing fluid, a packer fluid, animaging fluid, or a combination thereof.

In some embodiments, the composition further includes a saline, anaqueous base, an oil, an organic solvent, a synthetic fluid oil phase,an aqueous solution, an alcohol or a polyol, a cellulose, a starch, analkalinity control agent, an acidity control agent, a density controlagent, a density modifier, an emulsifier, a dispersant, a polymericstabilizer, a crosslinking agent, a polyacrylamide, a polymer, anantioxidant, a heat stabilizer, a foam control agent, a foaming agent, asolvent, a diluent, a plasticizer, a filler, an inorganic particle, apigment, a dye, a precipitating agent, a rheology modifier, anoil-wetting agent, a set retarding additive, a surfactant, a corrosioninhibitor, a gas, a weight reducing additive, a heavy-weight additive, alost circulation material, a filtration control additive, a salt, afiber, a thixotropic additive, a breaker, a crosslinker, a gas, arheology modifier, a curing accelerator, a curing retarder, a pHmodifier, a chelating agent, a scale inhibitor, an enzyme, a resin, awater control material, a polymer, an oxidizer, a marker, a Portlandcement, a pozzolana cement, a gypsum cement, a high alumina contentcement, a slag cement, a silica cement, a fly ash, a metakaolin, ashale, a zeolite, a crystalline silica compound, an amorphous silica, afiber, a hydratable clay, a microsphere, a pozzolan lime, orcombinations thereof.

In some embodiments, placing the composition in the subterraneanformation includes fracturing at least part of the subterraneanformation to form at least one subterranean fracture.

In some embodiments, the composition further includes a proppant, aresin-coated proppant, or a combination thereof.

In some embodiments, the placing of the composition in the subterraneanformation includes pumping the composition through a drill stringdisposed in a wellbore, through a drill bit at a downhole end of thedrill string, and back above-surface through an annulus. The method canfurther include, processing the composition exiting the annulus with atleast one fluid processing unit to generate a cleaned composition andrecirculating the cleaned composition through the wellbore.

Also, provided in this disclosure is a method of treating a subterraneanformation, the method including (i) placing in a subterranean formationa composition including (a) a coated nanoparticle including ananoparticle, a linker, and a stabilizing group and (b) a calcium ion.The linker includes a silane anchoring group and polyethylenimine. Thestabilizing group includes a propyl 1,2 diol. Further, the linker iscovalently bound to the nanoparticle and at least one amine of thepolyethylenimine is covalently bound to the propyl 1,2 diol stabilizinggroup.

In some embodiments, the composition includes sea water and the calciumion is present at a concentration at a concentration of about 0.05 M toabout 0.3 M. For example, the ion can be present at a concentration ofabout 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, or about 0.3M.

Also, provided in this disclosure is a method of treating a subterraneanformation, the method including (i) placing in a subterranean formationa composition including (a) a coated nanoparticle including a silicananoparticle, a linker, and a stabilizing group, and (b) a calcium ion.The linker includes a silane anchoring group and polyethylenimine. Thestabilizing group includes a propyl 1,2 diol. Further, the linker iscovalently bound to the nanoparticle and at least one amine of thepolyethylenimine is covalently bound to the propyl 1,2 diol stabilizinggroup.

In some embodiments, the composition includes sea water and the calciumion is present at a concentration at a concentration of about 0.05 M toabout 0.3 M. For example, the ion can be present at a concentration ofabout 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, or about 0.3M.

Compositions Including a Coated Nanoparticle.

Also, provided in this disclosure is a coated nanoparticle compositionincluding (i) a coated nanoparticle including a nanoparticle, a linker,and a stabilizing group and (ii) an ion. The linker includes a silaneanchoring group, a spacer, and a terminal group. Further, the silaneanchoring group is covalently bound to the nanoparticle core and atleast one of the terminal groups is covalently bound to at least onestabilizing group.

In some embodiments, the composition further includes an aqueous liquidincluding one or more of water, brine, produced water, flowback water,brackish water, fresh water, Arab-D-brine, sea water, mineral waters,and other waters of varying salinity and mineral concentration.

In some embodiments, the nanoparticle is selected from the groupconsisting of a silica nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andmixtures thereof. The nanoparticle can be a silica nanoparticle. Thelinker can include polyethylenimine. The stabilizing group can include afunctional group selected from the group consisting of:

and combinations thereof. The wavy line indicates a point of attachmentto the linker terminal group.

The ion can include one or more of a lithium ion, a sodium ion, apotassium ion, a silver ion, a magnesium ion, a calcium ion, a bariumion, a zinc ion, an aluminum ion, a bismuth ion, a copper (I) ion, acopper (II) ion, an iron (II) ion, an iron (III) ion, a tin (II) ion, atin (IV) ion, a chromium (II) ion, a chromium (III) ion, a manganese(II) ion, a manganese (III) ion, a mercury (I) ion, a mercury (II) ion,a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt (III) ion,a nickel ion (II), a nickel (IV) ion, a titanium ion, and a titanium(IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the ion is a calcium ion and is present in theaqueous liquid at a concentration at a concentration of about 0.05 M toabout 0.3 M. For example, the ion can be present at a concentration ofabout 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, or about 0.3M.

Also provided in this disclosure, is a coated nanoparticle compositionincluding (i) a coated nanoparticle including a silica nanoparticle, alinker, and a stabilizing group, and (ii) a calcium ion. The linkerincludes a silane anchoring group and polyethylenimine. The stabilizinggroup includes a propyl 1,2 diol. Further, the linker is covalentlybound to the nanoparticle and at least one amine of the polyethylenimineis covalently bound to the propyl 1,2 diol stabilizing group

Coated Nanoparticles.

Also provided in this disclosure, is a coated nanoparticle including (i)a nanoparticle, (ii) a linker including an anchoring group, a spacer,and a terminal group, and (iii) a stabilizing group. The anchoring groupis covalently bound to the nanoparticle core and at least one of theterminal groups is covalently bound to the stabilizing group.

Also provided in this disclosure is a coated nanoparticle including ananoparticle, a linker, and a stabilizing group. The linker includes asilane anchoring group and polyethylenimine. The stabilizing group caninclude a functional group selected from the group consisting of:

and combinations thereof.

Also provided in this disclosure is a coated nanoparticle including (i)a silica nanoparticle (ii) a linker including a silane anchoring groupand polyethylenimine, and (iii) a stabilizing group including propyl 1,2diol. The linker is covalently bound to the nanoparticle and at leastone amine of the polyethylenimine is covalently bound to the propyl 1,2diol stabilizing group.

Methods of Treating a Subterranean Formation with Crosslinked-CoatedNanoparticle Compositions

Also provided herein is a method of treating a subterranean formation.The method includes placing in placing in a subterranean formation acomposition including an ion and a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The coating includes a linker, a crosslinker, and a stabilizing group.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the linker is crosslinked by a crosslinker. Forexample, one or more linkers surrounding a nanoparticle can becrosslinked with a crosslinker, such as a bis-epoxide. Crosslinking oneor more linkers surrounding a nanoparticle with a crosslinker can ensurethe one or more linkers remain associated with the nanoparticle.

In some embodiments, the stabilizing group is covalently bound to thelinker. For example, a propyl 1,2 diol stabilizing group can beinstalled by reacting a polyethylenimine linker with glycidol.

In some embodiments, the linker is crosslinked with the crosslinker andthe linker is covalently bound to the stabilizing group. For example,the linker can be crosslinked with a a bis-epoxide, such as1,4-butanediol diglycidyl ether, and, subsequently, the crosslinkedlinker can be reacted with glycidol to install propyl 1,2 diolstabilizing groups.

The linker can include the subunit:

At each occurrence, the variable R¹ can be independently selected fromthe from the group consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canbe independently selected from a (C₁-C₁₀)alkyl interrupted with 0, 1, 2,3, or 4 oxygen atoms or substituted or unsubstituted nitrogen atoms.

In some embodiments, the linker terminal group is —OR^(A), —SR^(A),—N—NR^(A) ₂, O—NR^(A) ₂, or NR^(A) ₂. The variable R^(A), at eachoccurrence can be independently selected from —H or

The wavy line labeled 2 indicates a point of attachment to thestabilizing group.

In some embodiments the linker includes polyethylenimine. For examplethe linker can be a polyethylenimine with a weight-average MW (M_(w)) ofabout 500 Da, 1,000 Da, 2,000 Da, 5,000 Da, 10,000 Da, 15,000 Da, 20,000Da, 25,000 Da, 30,000 Da, 40,000 Da, or a Mw of about 50,000 Da. In someembodiments, the linker is polyethylenimine with a M_(w) of about 25,000Da.

The crosslinker can be an amine-reactive compound, such as apolyfunctional amine-reactive compound. The polyfunctionalamine-reactive compound polyfunctional amine-reactive compound can be ana substituted or unsubstituted dihaloalkane, a substituted orunsubstituted aralkyl dihalide, a substituted or unsubstituted alkylenediester, a substituted or unsubstituted aryl diester, a substituted orunsubstituted aralkyl diester, a substituted or unsubstituted alkylenediacylhalide, a substituted or unsubstituted aryl diacylhalide, asubstituted or unsubstituted aralkyl diacylhalide, a substituted orunsubstituted dialdehyde, a substituted or unsubstituted diepoxyalkane,a substituted or unsubstituted epihalohydrins, or a substituted orunsubstituted aralkyl diepoxide. For example, the polyfunctionalamine-reactive compound can include a diisocyanate, anepichlorohalohydrin, a triglycidyl ether, aromatic and aliphaticdialdehydes, bis(imido esters), bis(succinimidyl esters), diacidchloride, bis(acrylamides), dicarboxylic acids, or bis(enones).

The crosslinker can be a crosslinker that includes an epoxide functionalgroup. For example, the crosslinker can be a bis-epoxide. In someembodiments, the bis-epoxide crosslinker is a diglycidyl ether. Thediglycidyl ether can be include a 1,4-butanediol diglycidyl ether, apoly(ethylene glycol) diglycidyl ether, a neopentyl glycol diglycidylether, a glycerol diglycidyl ether, a 1,4-Cyclohexanedimethanoldiglycidyl ether, a resorcinol diglycidyl ether, a poly(propyleneglycol) diglycidyl ether, a bisphenol A diglycidyl ether, diglycidylether (C₆H₁₀O₃), a 1,2-propanediol diglycidyl ether, 1,4-butanediyldiglycidyl ether, or combinations thereof. In some embodiments, thediglycidyl ether is 1,4-butanediol diglycidyl ether.

The stabilizing group can include one or more of the followingfunctional groups: a —OH, a —CO₂H, a —CO₂CH₃, a phosphate, and asulfate. For example, the stabilizing group can include a functionalgroup selected from the group consisting of:

and combinations thereof. In some embodiments, the stabilizing group isa propyl 1,2 diol.

In some embodiments, the stabilizing group can be a carbohydrate. Forexample, the stabilizing group include at least one of a monosaccharide,an oligosaccharide, or a polysaccharide. In some embodiments, thepolysaccharide is selected from the group consisting of alginate,chitosan, curdlan, dextran, derivatized dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, diutan, welan, starch, derivatized starch, tamarind,tragacanth, guar gum, derivatized guar gum (for example, hydroxypropylguar, carboxy methyl guar, or carboxymethyl hydroxypropyl guar), gumghatti, gum arabic, locust bean gum, cellulose, and derivatizedcellulose (for example, carboxymethyl cellulose, hydroxyethyl cellulose,carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, or methylhydroxy ethyl cellulose). For example, the polysaccharide can bedextran.

The polysaccharide can have an average molecular weight of about 1,000Daltons (Da) to about 150,000 Da. For example, the polysaccharide canhave an average molecular weight of about 10,000 Da to about 140,000 Da,about 30,000 Da to about 130,000 Da, 50,000 to about 120,000 Da, 70,000Da to about 110,000 Da, or about 80,000 Da to about 100,000 Da, or about1,000 Da, 5,000 Da, 10,000 Da, 20,000 Da, 30,000 Da, 40,000 Da, 50,000Da, 60,000 Da, 70,000 Da, 80,000 Da, 90,000 Da, 100,000 Da, 110,000 Da,120,000 Da, 130,000 Da, 140,000 Da, or about 150,000 Da or greater.

In some embodiments, the crosslinked-coated nanoparticles have apositive zeta potential.

The nanoparticle can be a silica nanoparticle, a polymeric nanoparticle,a metal oxide nanoparticle, an upconverting nanoparticle, asuperparamagnetic nanoparticle, and mixtures thereof. In someembodiments, the nanoparticle is a polystyrene nanoparticle. Forexample, the nanoparticle can be a derivatized polystyrene nanoparticle,such as a sodium dodecyl sulfate (SDS) derivatized polystyrenicnanoparticle.

In some embodiments, the nanoparticle's surface is noncovalently boundto the linker. For example, the linker can electrostatically adsorb onthe surface of the nanoparticle. Electrostatic adsorption of a linker onthe surface of a nanoparticle can be accomplished by employing ananoparticle with a charged surface and a linker including oppositelycharged functional groups. For example, a polyethylenimine linker can beadsorbed on the surface of a negatively charged nanoparticle surface,such as a nanoparticle having a sodium dodecyl sulfate derivatizedsurface.

In some embodiments, the nanoparticle is selected from the groupconsisting of a silica nanoparticle, a metal oxide nanoparticle, asuperparamagnetic nanoparticle, an upconverting nanoparticle (e.g., rareearth upconverting nanoparticles), polymer-based nanoparticles such aspolystyrene based nanoparticles, carbonaceous nanoparticles such ascarbon black, carbon nanotubes, graphene, graphene platelets, andmixtures thereof. In some embodiments, the nanoparticle can include ametal oxide. In some embodiments, the nanoparticle includes an ironoxide, a nickel oxide, a cobalt oxide, a magnetite, a ferrite, orcombinations thereof. In some embodiments, the nanoparticle is asuperparamagnetic nanoparticle. Examples of superparamagneticnanoparticles include iron oxides, such as Fe₃O₄ and γ-Fe₂O₃, puremetals, such as Fe and Co, spinel-type ferromagnets, such as MgFe₂O₄,MnFe₂O₄, and CoFe₂O₄, as well as alloys, such as CoPt₃ and FePt. In someembodiments, the nanoparticle includes a fluoride. For example, thenanoparticle can include upconverting rare earth nanoparticles such asdoped YF4 nanoparticles. In some embodiments, the nanoparticle includesa metal oxide including an atom selected from the group consisting ofZn, Cr, Co, Dy, Er, Eu, Fe, Gd, Gd, Pr, Nd, Ni, In, Pr, Sm, Tb, Tm, andcombinations thereof.

In some embodiments, the nanoparticles have an average particle size ofabout 5 nm to about 1,000 nm. For example, the nanoparticles can have anaverage size of about 10 to 100 nm, 10 to 50 nm, or about 10 to 20 nm,as determined by scanning electron microscopy prior to forming thecrosslinked-coated nanoparticles. In some embodiments, the nanoparticleshave an average particle size of about 5 nm, 10 nm, 15 nm, 20 nm, 25 nm,30 nm, 50 nm, 75 nm, 100 nm, 150 nm, 200 nm, or about 250 nm. Forexample, the nanoparticles can have an average size of about 15 nm.

In some embodiments, the composition further includes an aqueous liquid.The aqueous liquid can include at least one of water, brine, producedwater, flowback water, bracking water, Arab-D-brine, fresh water,mineral waters, sea water, and other waters of varying salinity andmineral concentration. The aqueous liquid can include at least one of adrilling fluid, a fracturing fluid, a diverting fluid, an injectionfluid, and a lost circulation treatment fluid.

In some embodiments, method further includes obtaining or providing thecomposition, in which the obtaining or providing of the compositionoccurs above-surface. In some embodiments, the method further includesobtaining or providing the composition, in which the obtaining orproviding of the composition occurs in the subterranean formation. Forexample, the composition can be provided or obtained in the subterraneanformation by providing the crosslinked-coated nanoparticles from onesource and prior to, during, or after providing the crosslinked-coatednanoparticles, the ion can be provided from a separate source. Forexample, the ion could be initially provided in the subterraneanformation in an aqueous liquid and, subsequently, the crosslinked-coatednanoparticles could be provided to provide or obtain the composition.

In some embodiments, the method is at least one of a method of drillingthe subterranean formation, a method of fracturing the subterraneanformation, a method of conformance control, a method of subsurfaceimaging the subterranean formation, a method of aquifer remediation inthe subterranean formation.

In some embodiments, the crosslinked-coated nanoparticles have ahydrodynamic radius that is less than the hydrodynamic radius of similarnanoparticles without the cross-linked coating in a similar compositionunder similar conditions. For example, the crosslined-coatednanoparticles can have a hydrodynamic radius that is less than thehydrodynamic radius of similar nanoparticles without thecrosslinked-coating in a similar composition in water, brine, producedwater, flowback water, bracking water, Arab-D-brine, fresh water,mineral waters, sea water or mixtures thereof.

The crosslinked-coated nanoparticles, when at a concentration of about1,000 ppm in synthetic sea water, can have a hydrodynamic radius of lessthan about 250 nm, 200 nm, 150 nm, 100 nm, 75 nm, 50 nm, 40 nm, 30 nm,25 nm, or less than about 20 nm after heating at 90° C. in the syntheticsea water for 14 days. In some embodiments, the crosslinked-coatednanoparticles, when at a concentration of about 1,000 ppm in syntheticsea water, can have a hydrodynamic radius of less than about 30 nm afterheating at 90° C. in the synthetic sea water for 14 days. For example,crosslinked-coated nanoparticles synthesized from nanoparticles havingan average size of 15 nm, when at a concentration of about 1,000 ppm insynthetic sea water, can have a hydrodynamic radius of less than about25 nm after heating at 90° C. in the synthetic sea water for 14 days.For example,

In some embodiments, the composition includes an aqueous liquid and anion. The ion can be present at a concentration of about 0.01 M to about2 M. For example, the ion can be present at a concentration of about0.01 M, 0.02 M, 0.03 M, 0.04 M, 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M,0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1.0 M,1.5 M, or about 2 M. In some embodiments, the ion can be present at aconcentration of about 0.05 M to about 0.3 M. For example, the ion canbe present at a concentration of about 0.05 M, 0.06 M, 0.07 M, 0.08 M,0.09 M, 0.1 M, 0.2 M, or about 0.3 M. In some embodiments, the ion canbe present at a concentration of about 0.6 M to about 0.9 M. Forexample, the ion can be present at a concentration of about 0.6 M, 0.7M, 0.8 M, or about 0.9 M.

In some embodiments, the composition includes sea water and a calciumion where the calcium ion is present at a concentration at aconcentration of about 0.01 M to about 0.3 M. For example, the ion canbe present at a concentration of about 0.01 M, 0.02 M, 0.03 M, 0.04 M,0.05 M, 0.05 M, 0.06 M, 0.07 M, 0.08 M, 0.09 M, 0.1 M, 0.2 M, or about0.3 M.

The ions present in the composition can be closely associated with thestabilizing groups. For example, the ions present in the composition canbe bound to the stabilizing groups through non-covalent interactionssuch as through Van der Waals forces. Further, the ions present in thecomposition can be bound to the stabilizing groups through coordinatedbinding.

In some embodiments, the providing or obtaining the composition includesdetermining the presence and concentration of at least one ion of awater in a subterranean formation and doping the composition with thedetermined ion. For example, the composition can be doped with at leastone ion found in a water of a subterranean formation such that themolarity of the ion in the composition is at least 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, 80%, 85%, 90% or atleast 95% of the molarity of the ion found in the water of thesubterranean formation.

In some embodiments, the composition further includes a kosmotropic ion.In some embodiments, the method further includes aggregating andprecipitating the crosslinked-coated nanoparticles in the subterraneanformation by the addition of a kosmotropic ion, such as a sulfate, aphosphate, Mg²⁺, Li⁺, or any other suitable kosmotropic ion. In someembodiments, the method is a method of fluid diversion and furtherincludes aggregating, or aggregating and precipitating, thecrosslinked-coated nanoparticles in the subterranean formation by theaddition of a kosmotropic ion. In some embodiments, the method is amethod of conformance control and further includes aggregating, oraggregating and precipitating, of the coated nanoparticles in thesubterranean formation by the addition of a kosmotropic ion. Forexample, after the composition has been placed in the subterraneanformation a kosmotropic ion may be added to the composition. Addition ofthe kosmotropic ion can lead to aggregation, or aggregation andprecipitation, of the crosslinked-coated nanoparticles in thesubterranean formation. Such, compositions including kosmotropic ionsare useful in fluid diversion or conformance control.

In some embodiments, the composition further includes a chaotropic ion,such as urea, guanidinium chloride, lithium perchlorate, or any othersuitable chaotropic ion. In some embodiments, the method furtherincludes aggregating the crosslinked-coated nanoparticles at anoil-water interface. For example, the crosslinked-coated nanoparticlescan be aggregated at one or more oil-water interfaces by the addition ofa chaotropic ion, such as urea, guanidinium chloride, lithiumperchlorate, and any other suitable chaotropic ion.

In some embodiments, the composition further includes a counterion. Forexample, the counterion can be a halide, such as fluoro, chloro, iodo,or bromo. In other examples, the counterion can be nitrate, hydrogensulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate,iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide,amide, cyanate, hydroxide, permanganate. The counterion can be aconjugate base of any carboxylic acid, such as acetate or formate.

In some embodiments, the method further includes combining thecomposition with an aqueous or oil-based fluid including a drillingfluid, a stimulation fluid, a fracturing fluid, a spotting fluid, aclean-up fluid, a completion fluid, a remedial treatment fluid, anabandonment fluid, a pill, an acidizing fluid, a cementing fluid, apacker fluid, a imaging fluid or a combination thereof, to form amixture, in which the placing the composition in the subterraneanformation includes placing the mixture in the subterranean formation.When the composition is combined with an oil-based fluid, thecomposition can form emulsions.

In some embodiments, at least one of prior to, during, and after theplacing of the composition in the subterranean formation, thecomposition is used in the subterranean formation, at least one of aloneand in combination with other materials, as a drilling fluid, astimulation fluid, a fracturing fluid, a spotting fluid, a clean-upfluid, a completion fluid, a remedial treatment fluid, an abandonmentfluid, a pill, an acidizing fluid, a cementing fluid, a packer fluid, animaging fluid, or a combination thereof.

In some embodiments, the composition further includes a saline, anaqueous base, an oil, an organic solvent, a synthetic fluid oil phase,an aqueous solution, an alcohol or a polyol, a cellulose, a starch, analkalinity control agent, an acidity control agent, a density controlagent, a density modifier, an emulsifier, a dispersant, a polymericstabilizer, a crosslinking agent, a polyacrylamide, a polymer, anantioxidant, a heat stabilizer, a foam control agent, a foaming agent, asolvent, a diluent, a plasticizer, a filler, an inorganic particle, apigment, a dye, a precipitating agent, a rheology modifier, anoil-wetting agent, a set retarding additive, a surfactant, a corrosioninhibitor, a gas, a weight reducing additive, a heavy-weight additive, alost circulation material, a filtration control additive, a salt, afiber, a thixotropic additive, a breaker, a crosslinker, a gas, arheology modifier, a curing accelerator, a curing retarder, a pHmodifier, a chelating agent, a scale inhibitor, an enzyme, a resin, awater control material, a polymer, an oxidizer, a marker, a Portlandcement, a pozzolana cement, a gypsum cement, a high alumina contentcement, a slag cement, a silica cement, a fly ash, a metakaolin, ashale, a zeolite, a crystalline silica compound, an amorphous silica, afiber, a hydratable clay, a microsphere, a pozzolan lime, orcombinations thereof.

In some embodiments, placing the composition in the subterraneanformation includes fracturing at least part of the subterraneanformation to form at least one subterranean fracture.

In some embodiments, the composition further includes a proppant, aresin-coated proppant, or a combination thereof.

In some embodiments, the placing of the composition in the subterraneanformation includes pumping the composition through a drill stringdisposed in a wellbore, through a drill bit at a downhole end of thedrill string, and back above-surface through an annulus. The method canfurther include, processing the composition exiting the annulus with atleast one fluid processing unit to generate a cleaned composition andrecirculating the cleaned composition through the wellbore.

Crosslinked-Coated Nanoparticle Compositions

Also provided herein is a crosslinked-coated nanoparticle composition.The composition includes an ion and a crosslinked-coated nanoparticle.The crosslinked-coated nanoparticle includes a nanoparticle and acoating. The coating includes a linker, a crosslinker, and a stabilizinggroup.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

In some embodiments, the coating is non-covalently bound to thenanoparticle. For example, the coating can be electrostatically adsorbedon the nanoparticle.

The linker can be crosslinked with the crosslinker. The stabilizinggroup can be covalently bound to the linker. In some embodiments, thelinker is crosslinked with the crosslinker and the linker is covalentlybound to the stabilizing group.

In some embodiments, the linker includes the subunit:

At each occurrence, the variable R¹ cab be selected from the from thegroup consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canbe a (C₁-C₁₀)alkyl interrupted with 0, 1, 2, 3, or 4 oxygen atoms orsubstituted or unsubstituted nitrogen atoms.

The linker can include a terminal group that is selected from groupconsisting of OR^(A) ₂, —SR^(A) ₂, —N—NR^(A) ₂, O—NR^(A) ₂, and NR^(A)₂. The variable R², at each occurrence, can be independently selectedfrom —H or

The wavy line labeled 2 can indicate a point of attachment to thestabilizing group.

In some embodiments, the linker includes polyethylenimine.

The crosslinker can include an epoxide functional group. For example,the crosslinker can be a bis-epoxide. In some embodiments, thebis-epoxide is a diglycidyl ether. The diglycidyl ether can be selectedfrom the group consisting of a 1,4-butanediol diglycidyl ether, apoly(ethylene glycol) diglycidyl ether, a neopentyl glycol diglycidylether, a glycerol diglycidyl ether, a 1,4-Cyclohexanedimethanoldiglycidyl ether, a resorcinol diglycidyl ether, a poly(propyleneglycol) diglycidyl ether, a bisphenol A diglycidyl ether, diglycidylether (C₆H₁₀O₃), a 1,2-propanediol diglycidyl ether, 1,4-butanediyldiglycidyl ether, and combinations thereof. In some embodiments, thediglycidyl ether includes a 1,4-Butanediol diglycidyl ether.

The stabilizing group can include one or more of the followingfunctional groups a —OH, —CO₂H, —CO₂CH₃, a phosphate, or a sulfate. Insome embodiments, the stabilizing group includes a functional groupselected from the group consisting of:

and combinations thereof.

The nanoparticle can be selected from the group consisting of a silicananoparticle, a polymeric nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andcombinations thereof. In some embodiments, the nanoparticle is apolystyrene nanoparticle. The nanoparticle can also be a derivatizedpolystyrene nanoparticle. For example, the nanoparticle can be a sodiumdodecyl sulfate derivatized polystyrene nanoparticle.

In some embodiments, the nanoparticle includes a metal oxide. Forexample, the nanoparticle can include a metal oxide selected from thegroup consisting of an iron oxide, a nickel oxide, a cobalt oxide, amagnetite, a ferrite, and combinations thereof. The nanoparticle caninclude a metal oxide including an atom selected from the groupconsisting of Zn, Cr, Co, Dy, Er, Eu, Gd, Gd, Pr, Nd, In, Pr, Sm, Tb,Tm, and combinations thereof. In some embodiments, the nanoparticleincludes a superparamagnetic metal oxide.

Also provided herein is a crosslinked-coated nanoparticle composition.The composition includes an ion and a crosslinked-coated nanoparticle.The crosslinked-coated nanoparticle includes a nanoparticle and acoating. The nanoparticle surface has an overall negative charge. Thecoating includes a polyethylene amine crosslinked with a bis-epoxidecrosslinker, and a stabilizing group. In some embodiments, thestabilizing group is a propyl 1,2 diol. The propyl 1,2 diol can beinstalled by reacting the cross-linked polyethylenimine with glycidol.

In some embodiments, the ion includes one or more of a lithium ion, asodium ion, a potassium ion, a silver ion, a magnesium ion, a calciumion, a barium ion, a zinc ion, an aluminum ion, a bismuth ion, a copper(I) ion, a copper (II) ion, an iron (II) ion, an iron (III) ion, a tin(II) ion, a tin (IV) ion, a chromium (II) ion, a chromium (III) ion, amanganese (II) ion, a manganese (III) ion, a mercury (I) ion, a mercury(II) ion, a lead (II) ion, a lead (IV) ion, a cobalt (II) ion, a cobalt(III) ion, a nickel ion (II), a nickel (IV) ion, a titanium ion, and atitanium (IV) ion. For example, the ion can include a calcium ion.

Also provided herein is a crosslinked-coated nanoparticle composition.The composition includes a calcium ion and a crosslinked-coatednanoparticle. The crosslinked-coated nanoparticle includes ananoparticle and a coating. The nanoparticle surface has an overallnegative charge. The crosslinked-coated nanoparticle includes ananoparticle and a coating. The coating includes a polyethylene aminecrosslinked with a bis-epoxide crosslinker, and a propyl 1,2 diolstabilizing group.

Also provided herein is a crosslinked-coated nanoparticle composition.The composition includes a calcium ion and a crosslinked-coatednanoparticle. The crosslinked-coated nanoparticle includes ananoparticle and a coating. The nanoparticle surface has an overallnegative charge. The coating includes polyethylene amine crosslinkedwith a 1,4-butanediol diglycidyl ether crosslinker, and a propyl 1,2diol stabilizing group.

Crosslinked-Coated Nanoparticles.

Also provided herein is a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a crosslinked-coatednanoparticle comprising a nanoparticle and a coating, The coatingincludes a linker, a crosslinker, and a stabilizing group.

In some embodiments, the coating is non-covalently bound to thenanoparticle. For example, the coating can be electrostatically adsorbedon the nanoparticle.

The linker can be crosslinked with the crosslinker. The stabilizinggroup can be covalently bound to the linker. In some embodiments, thelinker is crosslinked with the crosslinker and the linker is covalentlybound to the stabilizing group.

In some embodiments, the linker includes the subunit:

At each occurrence, the variable R¹ cab be selected from the from thegroup consisting of —H,

or a linear or branched (C₁-C₂₀)alkyl interrupted with 0, 1, 2, 3, 4, 5,6, 7, 8, or 9 substituted or unsubstituted nitrogen atoms. The wavy linelabeled 1 can indicate a point of attachment to another linker on thecrosslinked-coated nanoparticle. At each occurrence, the variable A canbe a (C₁-C₁₀)alkyl interrupted with 0, 1, 2, 3, or 4 oxygen atoms orsubstituted or unsubstituted nitrogen atoms.

The linker can include a terminal group that is selected from groupconsisting of 0102, —SR^(A) ₂, —N—NR^(A) ₂, O—NR^(A) ₂, and NR^(A) ₂.The variable R², at each occurrence, can be independently selected from—H or

The wavy line labeled 2 can indicate a point of attachment to thestabilizing group.

In some embodiments, the linker includes polyethylenimine.

The crosslinker can include an epoxide functional group. For example,the crosslinker can be a bis-epoxide. In some embodiments, thebis-epoxide is a diglycidyl ether. The diglycidyl ether can be selectedfrom the group consisting of a 1,4-butanediol diglycidyl ether, apoly(ethylene glycol) diglycidyl ether, a neopentyl glycol diglycidylether, a glycerol diglycidyl ether, a 1,4-Cyclohexanedimethanoldiglycidyl ether, a resorcinol diglycidyl ether, a poly(propyleneglycol) diglycidyl ether, a bisphenol A diglycidyl ether, diglycidylether, a 1,2-propanediol diglycidyl ether, 1,4-butanediyl diglycidylether, and combinations thereof. In some embodiments, the diglycidylether includes a 1,4-Butanediol diglycidyl ether.

The stabilizing group can include one or more of the followingfunctional groups a —OH, —CO₂H, —CO₂CH₃, a phosphate, or a sulfate. Insome embodiments, the stabilizing group includes a functional groupselected from the group consisting of:

and combinations thereof.

The nanoparticle can be selected from the group consisting of a silicananoparticle, a polymeric nanoparticle, a metal oxide nanoparticle, anupconverting nanoparticle, a superparamagnetic nanoparticle, andcombinations thereof. In some embodiments, the nanoparticle is apolystyrene nanoparticle. The nanoparticle can also be a derivatizedpolystyrene nanoparticle. For example, the nanoparticle can be a sodiumdodecyl sulfate derivatized polystyrene nanoparticle.

In some embodiments, the nanoparticle includes a metal oxide. Forexample, the nanoparticle can include a metal oxide selected from thegroup consisting of an iron oxide, a nickel oxide, a cobalt oxide, amagnetite, a ferrite, and combinations thereof. The nanoparticle caninclude a metal oxide including an atom selected from the groupconsisting of Zn, Cr, Co, Dy, Er, Eu, Gd, Gd, Pr, Nd, In, Pr, Sm, Tb,Tm, and combinations thereof. In some embodiments, the nanoparticleincludes a superparamagnetic metal oxide.

Also provided herein is a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The nanoparticle surface has an overall negative charge. The coatingincludes a polyethylene amine crosslinked with a bis-epoxidecrosslinker, and a stabilizing group. In some embodiments, thestabilizing group is a propyl 1,2 diol. The propyl 1,2 diol can beinstalled by reacting the cross-linked polyethylenimine with glycidol.

Also provided herein is a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The nanoparticle surface has an overall negative charge. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The coating includes a polyethylene amine crosslinked with a bis-epoxidecrosslinker, and a propyl 1,2 diol stabilizing group.

Also provided herein is a crosslinked-coated nanoparticle. Thecrosslinked-coated nanoparticle includes a nanoparticle and a coating.The nanoparticle surface has an overall negative charge. The coatingincludes polyethylene amine crosslinked with a 1,4-butanediol diglycidylether crosslinker, and a propyl 1,2 diol stabilizing group.

Other Components

The composition including the nanoparticles (e.g., coated nanoparticlesand crosslinked-coated nanoparticles) and the ion, can further includeone or more suitable components. The additional components can be anycomponents, such that the composition can be used as described in thisdisclosure.

In some embodiments, the composition includes one or more viscosifiers.The viscosifier can be any suitable viscosifier. The viscosifier canaffect the viscosity of the composition or a solvent that contacts thecomposition at any suitable time and location. In some embodiments, theviscosifier provides an increased viscosity at least one of beforeinjection into the subterranean formation, at the time of injection intothe subterranean formation, during travel through a tubular disposed ina borehole, once the composition reaches a particular subterraneanlocation, or some period of time after the composition reaches aparticular subterranean location. In some embodiments, the viscosifiercan be about 0.0001 wt % to about 10 wt % of the composition.

The viscosifier can include at least one of a linear polysaccharide, andpoly((C₂-C₁₀)alkenylene), in which at each occurrence, the(C₂-C₁₀)alkenylene is independently substituted or unsubstituted. Insome embodiments, the viscosifier can include at least one ofpoly(acrylic acid) or (C₁-C₅)alkyl esters thereof, poly(methacrylicacid) or (C₁-C₅)alkyl esters thereof, poly(vinyl acetate), poly(vinylalcohol), poly(ethylene glycol), poly(vinyl pyrrolidone),polyacrylamide, poly (hydroxyethyl methacrylate), alginate, chitosan,curdlan, dextran, emulsan, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, welan, derivatized starch, tamarind, tragacanth, guar gum,derivatized guar (for example, hydroxypropyl guar, carboxy methyl guar,or carboxymethyl hydroxylpropyl guar), gum ghatti, gum arabic, locustbean gum, and derivatized cellulose (for example, carboxymethylcellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose,hydroxypropyl cellulose, or methyl hydroxyl ethyl cellulose).

The viscosifier can include a poly(vinyl alcohol) homopolymer,poly(vinyl alcohol) copolymer, a crosslinked poly(vinyl alcohol)homopolymer, and a crosslinked poly(vinyl alcohol) copolymer. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof a substituted or unsubstituted (C₂-C₅₀)hydrocarbyl having at leastone aliphatic unsaturated C—C bond therein, and a substituted orunsubstituted (C₂-C₅₀)alkene. The viscosifier can include a poly(vinylalcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymerincluding at least one of a graft, linear, branched, block, and randomcopolymer of vinyl alcohol and at least one of vinyl phosphonic acid,vinylidene diphosphonic acid, substituted or unsubstituted2-acrylamido-2-methylpropanesulfonic acid, a substituted orunsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid,pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoicacid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid,acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid,vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid,crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid,allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and asubstituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate,vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, andvinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted(C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoicanhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substitutedor unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride,butenoic acid anhydride, pentenoic acid anhydride, hexenoic acidanhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoicacid anhydride, acrylic acid anhydride, fumaric acid anhydride,methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinylphosphonic acid anhydride, vinylidene diphosphonic acid anhydride,itaconic acid anhydride, crotonic acid anhydride, mesoconic acidanhydride, citraconic acid anhydride, styrene sulfonic acid anhydride,allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinylsulfonic acid anhydride, and an N—(C₁-C₁₀)alkenyl nitrogen containingsubstituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier caninclude a poly(vinyl alcohol) copolymer or a crosslinked poly(vinylalcohol) copolymer including at least one of a graft, linear, branched,block, and random copolymer that includes apoly(vinylalcohol)-poly(acrylamide) copolymer, apoly(vinylalcohol)-poly(2-acrylamido-2-methylpropanesulfonic acid)copolymer, or a poly(vinylalcohol)-poly(N-vinylpyrrolidone) copolymer.The viscosifier can include a crosslinked poly(vinyl alcohol)homopolymer or copolymer including a crosslinker including at least oneof chromium, aluminum, antimony, zirconium, titanium, calcium, boron,iron, silicon, copper, zinc, magnesium, and an ion thereof. Theviscosifier can include a crosslinked poly(vinyl alcohol) homopolymer orcopolymer including a crosslinker including at least one of an aldehyde,an aldehyde-forming compound, a carboxylic acid or an ester thereof, asulfonic acid or an ester thereof, a phosphonic acid or an esterthereof, an acid anhydride, and an epihalohydrin.

The composition can further include a crosslinker. The crosslinker canbe any suitable crosslinker. The crosslinker can be present in anysuitable concentration, such as more, less, or an equal concentration ascompared to the concentration of the crosslinker. In some embodiments,the crosslinker can include at least one of chromium, aluminum,antimony, zirconium, titanium, calcium, boron, iron, silicon, copper,zinc, magnesium, and an ion thereof. The crosslinker can include atleast one of boric acid, borax, a borate, a (C₁-C₃₀)hydrocarbylboronicacid, a (C₁-C₃₀)hydrocarbyl ester of a (C₁-C₃₀)hydrocarbylboronic acid,a (C₁-C₃₀)hydrocarbylboronic acid-modified polyacrylamide, ferricchloride, disodium octaborate tetrahydrate, sodium metaborate, sodiumdiborate, sodium tetraborate, disodium tetraborate, a pentaborate,ulexite, colemanite, magnesium oxide, zirconium lactate, zirconiumtriethanol amine, zirconium lactate triethanolamine, zirconiumcarbonate, zirconium acetylacetonate, zirconium malate, zirconiumcitrate, zirconium diisopropylamine lactate, zirconium glycolate,zirconium triethanol amine glycolate, zirconium lactate glycolate,titanium lactate, titanium malate, titanium citrate, titanium ammoniumlactate, titanium triethanolamine, titanium acetylacetonate, aluminumlactate, and aluminum citrate. The composition can include any suitableproportion of the crosslinker, such as about 0.1 wt % to about 50 wt %,or about 0.1 wt % to about 20 wt %, or about 0.001 wt %, 0.01, 0.1, 1,2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94,95, 96, 97, 98, or about 99 wt % or more of the composition.

In some embodiments, the composition, or a mixture including the same,can include any suitable amount of any suitable material used in adownhole fluid. For example, the composition or a mixture including thesame can include water, saline, aqueous base, acid, oil, organicsolvent, synthetic fluid oil phase, aqueous solution, alcohol or polyol,cellulose, starch, alkalinity control agents, acidity control agents,density control agents, density modifiers, emulsifiers, dispersants,polymeric stabilizers, crosslinking agents, polyacrylamide, a polymer orcombination of polymers, antioxidants, heat stabilizers, foam controlagents, solvents, diluents, plasticizer, filler or inorganic particle,pigment, dye, precipitating agent, rheology modifier, oil-wettingagents, set retarding additives, surfactants, gases, weight reducingadditives, heavy-weight additives, lost circulation materials,filtration control additives, salts (for example, any suitable salt,such as potassium salts such as potassium chloride, potassium bromide,potassium formate; calcium salts such as calcium chloride, calciumbromide, calcium formate; cesium salts such as cesium chloride, cesiumbromide, cesium formate, or a combination thereof), fibers, thixotropicadditives, breakers, crosslinkers, rheology modifiers, curingaccelerators, curing retarders, pH modifiers, chelating agents, scaleinhibitors, enzymes, resins, water control materials, oxidizers,markers, Portland cement, pozzolana cement, gypsum cement, high aluminacontent cement, slag cement, silica cement, fly ash, metakaolin, shale,zeolite, a crystalline silica compound, amorphous silica, hydratableclays, microspheres, lime, or a combination thereof.

A drilling fluid, also known as a drilling mud or simply “mud,” is aspecially designed fluid that is circulated through a wellbore as thewellbore is being drilled to facilitate the drilling operation. Thedrilling fluid can be water-based or oil-based. The drilling fluid cancarry cuttings up from beneath and around the bit, transport them up theannulus, and allow their separation. Also, a drilling fluid can cool andlubricate the drill head as well as reduce friction between the drillstring and the sides of the hole. The drilling fluid aids in support ofthe drill pipe and drill head, and provides a hydrostatic head tomaintain the integrity of the wellbore walls and prevent well blowouts.Specific drilling fluid systems can be selected to optimize a drillingoperation in accordance with the characteristics of a particulargeological formation. The drilling fluid can be formulated to preventunwanted influxes of formation fluids from permeable rocks and also toform a thin, low permeability filter cake that temporarily seals pores,other openings, and formations penetrated by the bit. In water-baseddrilling fluids, solid particles are suspended in a water or brinesolution containing other components. Oils or other non-aqueous liquidscan be emulsified in the water or brine or at least partiallysolubilized (for less hydrophobic non-aqueous liquids), but water is thecontinuous phase. A drilling fluid can be present in the mixture withthe composition including the crosslinkable ampholyte polymer and thecrosslinker, or a crosslinked reaction product thereof, in any suitableamount, such as about 1 wt % or less, about 2 wt %, 3, 4, 5, 10, 15, 20,30, 40, 50, 60, 70, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, 99.999,or about 99.9999 wt % or more of the mixture.

A water-based drilling fluid in methods provided in this disclosure canbe any suitable water-based drilling fluid. In some embodiments, thedrilling fluid can include at least one of water (fresh or brine), asalt (for example, calcium chloride, sodium chloride, potassiumchloride, magnesium chloride, calcium bromide, sodium bromide, potassiumbromide, calcium nitrate, sodium formate, potassium formate, cesiumformate), aqueous base (for example, sodium hydroxide or potassiumhydroxide), alcohol or polyol, cellulose, starches, alkalinity controlagents, density control agents such as a density modifier (for example,barium sulfate), surfactants (for example, betaines, alkali metalalkylene acetates, sultaines, ether carboxylates), emulsifiers,dispersants, polymeric stabilizers, crosslinking agents,polyacrylamides, polymers or combinations of polymers, antioxidants,heat stabilizers, foam control agents, foaming agents, solvents,diluents, plasticizers, filler or inorganic particles (for example,silica), pigments, dyes, precipitating agents (for example, silicates oraluminum complexes), and rheology modifiers such as thickeners orviscosifiers (for example, xanthan gum). Any ingredient listed in thisparagraph can be either present or not present in the mixture.

An oil-based drilling fluid or mud in methods provided in thisdisclosure can be any suitable oil-based drilling fluid. In someembodiments the drilling fluid can include at least one of an oil-basedfluid (or synthetic fluid), saline, aqueous solution, emulsifiers, otheragents of additives for suspension control, weight or density control,oil-wetting agents, fluid loss or filtration control agents, andrheology control agents. For example, see H. C. H. Darley and George R.Gray, Composition and Properties of Drilling and Completion Fluids66-67, 561-562 (5th ed. 1988). An oil-based or invert emulsion-baseddrilling fluid can include between about 10:90 to about 95:5, or about50:50 to about 95:5, by volume of oil phase to water phase. Asubstantially all oil mud includes about 100% liquid phase oil by volume(for example, substantially no internal aqueous phase).

A pill is a relatively small quantity (for example, less than about 500bbl, or less than about 200 bbl) of drilling fluid used to accomplish aspecific task that the regular drilling fluid cannot perform. Forexample, a pill can be a high-viscosity pill to, for example, help liftcuttings out of a vertical wellbore. In another example, a pill can be afreshwater pill to, for example, dissolve a salt formation. Anotherexample is a pipe-freeing pill to, for example, destroy filter cake andrelieve differential sticking forces. In another example, a pill is alost circulation material pill to, for example, plug a thief zone. Apill can include any component described in this disclosure as acomponent of a drilling fluid.

A cement fluid can include an aqueous mixture of at least one of cementand cement kiln dust. The composition including the crosslinkableampholyte polymer and the crosslinker, or a crosslinked reaction productthereof, can form a useful combination with cement or cement kiln dust.The cement kiln dust can be any suitable cement kiln dust. Cement kilndust can be formed during the manufacture of cement and can be partiallycalcined kiln feed that is removed from the gas stream and collected ina dust collector during a manufacturing process. Cement kiln dust can beadvantageously utilized in a cost-effective manner since kiln dust isoften regarded as a low value waste product of the cement industry. Someembodiments of the cement fluid can include cement kiln dust but nocement, cement kiln dust and cement, or cement but no cement kiln dust.The cement can be any suitable cement. The cement can be a hydrauliccement. A variety of cements can be utilized in accordance withembodiments of the methods described in this disclosure; for example,those including calcium, aluminum, silicon, oxygen, iron, or sulfur,which can set and harden by reaction with water. Suitable cements caninclude Portland cements, pozzolana cements, gypsum cements, highalumina content cements, slag cements, silica cements, and combinationsthereof. In some embodiments, the Portland cements that are suitable foruse in embodiments of the methods described in this disclosure areclassified as Classes A, C, H, and G cements according to the AmericanPetroleum Institute, API Specification for Materials and Testing forWell Cements, API Specification 10, Fifth Ed., Jul. 1, 1990. A cementcan be generally included in the cementing fluid in an amount sufficientto provide the desired compressive strength, density, or cost. In someembodiments, the hydraulic cement can be present in the cementing fluidin an amount in the range of from 0 wt % to about 100 wt %, 0-95 wt %,20-95 wt %, or about 50-90 wt %. A cement kiln dust can be present in anamount of at least about 0.01 wt %, or about 5 wt %-80 wt %, or about 10wt % to about 50 wt %.

Optionally, other additives can be added to a cement or kilndust-containing composition of embodiments of the methods described inthis disclosure as deemed appropriate by one skilled in the art, withthe benefit of this disclosure. Any optional ingredient listed in thisparagraph can be either present or not present in the composition. Forexample, the composition can include fly ash, metakaolin, shale,zeolite, set retarding additive, surfactant, a gas, accelerators, weightreducing additives, heavy-weight additives, lost circulation materials,filtration control additives, dispersants, and combinations thereof. Insome examples, additives can include crystalline silica compounds,amorphous silica, salts, fibers, hydratable clays, microspheres,pozzolan lime, thixotropic additives, combinations thereof, and thelike.

The composition or mixture can further include a proppant such as aresin-coated proppant, an encapsulated resin, or a combination thereof.A proppant is a material that keeps an induced hydraulic fracture atleast partially open during or after a fracturing treatment. Proppantscan be transported into the subterranean formation and to the fractureusing fluid, such as fracturing fluid or another fluid. Ahigher-viscosity fluid can more effectively transport proppants to adesired location in a fracture, especially larger proppants, by moreeffectively keeping proppants in a suspended state within the fluid.Examples of proppants can include sand, gravel, glass beads, polymerbeads, ground products from shells and seeds such as walnut hulls, andmanmade materials such as ceramic proppant, bauxite, tetrafluoroethylenematerials (for example, TEFLON™ available from DuPont), fruit pitmaterials, processed wood, composite particulates prepared from a binderand fine grade particulates such as silica, alumina, fumed silica,carbon black, graphite, mica, titanium dioxide, meta-silicate, calciumsilicate, kaolin, talc, zirconia, boron, fly ash, hollow glassmicrospheres, and solid glass, or mixtures thereof. In some embodiments,proppant can have an average particle size, in which particle size isthe largest dimension of a particle, of about 0.001 mm (millimeters) toabout 3 mm, about 0.15 mm to about 2.5 mm, about 0.25 mm to about 0.43mm, about 0.43 mm to about 0.85 mm, about 0.85 mm to about 1.18 mm,about 1.18 mm to about 1.70 mm, or about 1.70 to about 2.36 mm. In someembodiments, the proppant can have a distribution of particle sizesclustering around multiple averages, such as one, two, three, or fourdifferent average particle sizes. The composition or mixture can includeany suitable amount of proppant, such as about 0.0001 wt % to about 99.9wt %, about 0.1 wt % to about 80 wt %, or about 10 wt % to about 60 wt%, or about 0.00000001 wt % or less, or about 0.000001 wt %, 0.0001,0.001, 0.01, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9 wt %, or about 99.99 wt %or more.

System or Apparatus

Also provided in this disclosure, is a system including a nanoparticlecomposition including a nanoparticle, an ion, and a subterraneanformation including the composition therein. The nanoparticle can be acoated nanoparticle, as described in this disclosure, or acrosslinked-coated nanoparticle as describe in this disclosure.

In some embodiments, the composition in the system can also include adownhole fluid, or the system can include a mixture of the compositionand downhole fluid. In some embodiments, the system can include atubular, and a pump configured to pump the composition into thesubterranean formation through the tubular.

In some embodiments, the system can include a pump fluidly coupled to atubular (for example, any suitable type of oilfield pipe, such aspipeline, drill pipe, production tubing, and the like), the tubularcontaining a composition including the coated nanoparticle and the ion,described in this disclosure.

In some embodiments, the system can include a drillstring disposed in awellbore, the drillstring including a drill bit at a downhole end of thedrillstring. The system can include an annulus between the drillstringand the wellbore. The system can also include a pump configured tocirculate the composition through the drill string, through the drillbit, and back above-surface through the annulus. The system can includea fluid processing unit configured to process the composition exitingthe annulus to generate a cleaned drilling fluid for recirculationthrough the wellbore.

EXAMPLES Example 1. Glycidylated-Polyethylenimine Silica Nanoparticlesand Polyethylenimine Silica Nanoparticles

Synthesis of Coated Nanoparticles

Materials.

Tetraethylorthosilicate 98% (Sigma Aldrich), tetramethylrhodamine-5-(and6)-C2, maleimide (Anaspec), L-Arginine 98% (Sigma Aldrich),(3-Mercaptopropyl) trimethoxysilane 95% (Gelest), trimethoxysilylpropylmodified (polyethylenimine) (PEI-silane), 50% in isopropanol (Gelest),glycidol (Acros Organics), tris Buffered Saline (TBS), 1× solution (pH7.4/Molecular Biology), (Fisher BioReagents) ultrapure water.

25 nm and 45 nm Fluorescent Silica Nanoparticle Synthesis.

25 nm fluorescent silica nanoparticles “seeds” were synthesized basedupon a modified protocol that was described in Hartlen et al. (Langmuir2008, 24 (5), 1714-1720). The following description was for a batchsynthesis of 50 mL volume. Briefly, dye precursor was prepared fromreacting 20 molar excess of (3-Mercaptopropyl) trimethoxysilane withtetramethylrhodamine-5-(and 6)-C2 maleimide at a dye stock concentrationof 4.5 mM. For a 50 mL batch, 400 uL of dye precursor was prepared. In around bottom (RB) flask, 40.8 mL of ultrapure water was heated to 60° C.and stirred at 150 RPM on a magnetic stir plate. 5.78 mL of 10 mg/mLL-arginine stock solution was added into the RB flask and lethomogenize. On Day 1, two 100 uL aliquots of dye precursor were addedinto the flask followed with 675 uL of tetraethylorthosilicate (TEOS)with at least 8 hours between additions. On Day 2, the same addition ofdye precursor and TEOS was repeated. On Day 3, 717 uL of TEOS was addedinto the RB flask and the reaction is allowed to proceed overnight.

45 nm fluorescent silica nanoparticles were synthesized using theaforementioned 25 nm seeds. For a typical 100 mL, 20 mL of 25 nm seedswas added to 80 mL of ultrapure water and heated to 60° C. and stirredat 150 RPM. 2.16 mL of 4.5 mM dye precursor and 5.4 mL TEOS will beadded in 8 aliquots of 270 uL and 675 uL respectively over 8 days. Onthe ninth day, 1.4 mL was added to the RB flask and the reaction wasallowed to proceed overnight. This yielded a 22 mg/mL suspension.

Coating 45 nm Fluorescent Silica Nanoparticles with PEI-Silane.

To coat 50 mL of 45 nm fluorescent silica nanoparticles withtrimethoxysilylpropyl modified (polyethylenimine) (PEI-silane), 37.5 mLof the 50% PEI-silane solution was added to 62.5 mL ultrapure water andstirred at 900 RPM in an RB flask. Into this solution, the 45 nmnanoparticle suspension was added in 125 aliquots of 400 uL atone-minute interval between additions. At the completion of theaddition, the suspension was heated to 85° C. overnight. FIG. 1 shows arepresentative scanning electron micrograph for 45 nm fluorescentnanoparticles after PEI-coating.

Removal of Excess PEI-Silane.

Two methods were used to remove excess PEI-silane from the reactionmixture post coating.

First, centrifugation devices with 100 kD molecular weight cut-off(MWCO) polyethersulfone (PES) membrane were employed. The suspension wasloaded into the centrifugation devices and spun at 5000 RPM for 30minutes. The filtrate was discarded and the retentate resuspended inultrapure water. This treatment was repeated 5 times. The finalretentate was reconstituted to approximately 22 mg/mL (the originalnanoparticle solid content).

Alternatively, a cross-flow diafiltration with PES hollow-fiber membraneat 500 kD MWCO was employed. Typically, a 200 mL-coating batch atnominal concentration of 4.4 mg/mL as described above in “Coating 45 nmFluorescent Silica Nanoparticles with PEI-silane” was subjected topurification with 2 L water. The feed rate was set at 30 mL/min with thetransmembrane pressure kept at approximately 1 psi. At the end of thediafiltration process, the suspension was reconcentrated to theapproximately 22 mg/mL (the original nanoparticle solid content).

Glycidol Surface Modification.

10 mL aqueous suspension of 22 mg/mL PEI-coated nanoparticles weretypically modified with 200 uL of technical grade glycidol at roomtemperature. The reaction solution was stirred rigorously and allowed toproceed overnight. The solution was then quenched with 2 mL Tris-HClbuffer solution before further purification via diafiltration asdescribed above.

FIG. 2 is a schematic of the surface chemistry of the nanoparticles (a)after PEI coating and (b) after glycidol modification of PEI.Glycidylation of the PEI polymer resulted in a polyol coating on thenanoparticles. FIG. 3 depicts the hydrodynamic diameter of silicananoparticles with neat, PEI-coated and glycidylated surfaces.

Table 2 details the synthetic brine compositions used for stimulatedreservoir environment testing.

TABLE 2 Sea Water (mol/L) Arab-D Brine (mol/L) NaCl 0.7022 1.2764CaCl₂•2H₂0 0.0162 0.3387 MgCl₂•6H₂O 0.0868 0.0648 BaCl₂ 0.00 0.0001Na₂SO₄ 0.0447 0.0042 NaHCO₃ 0.0020 0.00607 Na₂CO₃ 0.00 0.00Colloidal Stability.

Solution Preparation. 10 mL of 1000 ppm suspensions were prepared indeionized water, synthetic seawater and Arab-D brine by diluting thestock 22,000 ppm (˜22 mg/mL) solution into the brine solutions with thecompositions. 5 mL was pipetted into glass pressure tubes with orwithout 1 g crushed Arab-D rocks. The tubes were crimped with aluminumcaps with PTFE-lined septa. The remainder of the solutions was reservedas room temperature controls.

Static Stability Testing. All samples were placed in the oven at 90° C.On Day 3, samples with crushed reservoir rocks were shaken briefly. OnDay 8, all samples were removed from the oven, documentedphotographically and characterized via dynamic light scattering andUV-Vis Spectrophotometry.

Dynamic Light Scattering (DLS). All samples were measured at 1000 ppmwithout filtration or dilution. For each sample, five measurements attwo minutes acquisition time were taken. No adjustments in solutionviscosity in the measurement parameters were made for the samples inbrine. For samples with visible precipitation, DLS measurements were notperformed.

UV-Vis Spectrometry. For samples that exhibited good colloidalstability, UV-Vis absorbance of the samples was taken from 250 nm to 800nm after transferring a 1:3 dilution of the 1,000 ppm solution in eitherdeionized, seawater or Arab-D brine into UV-transparent plasticcuvettes. Adsorption rates to crushed Arab-D rocks were calculated fromabsorbance maximum of tetramethylrhodamine at 550 nm.

Colloidal Stability in Arab-D Low Salinity Brine.

Photon correlation spectroscopy (dynamic light scattering) was used tomeasure the colloidal stability of the nanoparticles in Arab-D brineafter treating the nanoparticles to 8 days at 90° C. Results indicatedthat PEI-coated nanoparticles have aggregated FIG. 4(b), whereas thecolloidal stability of the glycidylated PEI-coated nanoparticle wasexcellent over the test duration. Glycidylated nanoparticles stayed insuspension over a one-month period.

FIG. 4 shows a comparison of colloidal stability of the nanoparticles inArab-D brine at 90° C. for 8 days shows that the glycidylatednanoparticles remain stable over the testing period (a), whereas the (b)PEI-coated nanoparticles have grown in size (aggregation).

Adsorption to Reservoir Rocks.

To determine the propensity of the glycidylated PEI coating chemistry toadhere to carbonate reservoir rocks, a static test was performed wherethe nanoparticle suspension in Arab-D brine was incubated withapproximately 20 wt % (1 g in 5 mL suspension) finely crushed carbonaterocks at 90° C. At the end of Day 8, the absorbance of the suspensionwas compared with both nanoparticles suspensions in Arab-D brine at roomtemperature and at 90° C. Absorbance maxima of the encapsulated dye,tetramethylrhodamine, of the three suspensions were used to determine19% loss to rock adsorption.

FIG. 5 shows absorbance maximum at 550 nm of tetramethylrhodamine, theencapsulated dye, was used to quantitate rock adsorption in the staticstability test. After 8 days in Arab-D brine interfaced with finelycrushed carbonate reservoir rocks, a loss of 19% loss to rock adsorptionwas determined.

Long-Term Colloidal Stability and Minimized Rock Adhesion.

FIG. 6 shows that after 21 days at 90° C., glycidylated PEInanoparticles are still well suspended above crushed rocks whereas thePEI coated nanoparticles have fallen out of suspension.

Stability in Seawater.

During the course of the testing, it was discovered that thenanoparticles were unstable in seawater. FIG. 7 shows that after 8 daysat 90° C. in seawater, the nanoparticles have aggregated (sizeincrease). The relatively high concentration of magnesium ions and lowerconcentration of calcium ions in seawater were determined to be thefactors in the root cause analysis. It was necessary to add a lowconcentration of additional calcium ions to the seawater to mitigatenanoparticle aggregation, as shown in FIG. 8. This is due to thespecific ion interactions of the coating with the constituents of thebrine compositions. While Arab-D brine and seawater contains similarlevels of magnesium ions in its composition (Table 2), the difference instability of the nanoparticles in seawater and Arab-D brine can beattributed to the far higher concentration (˜20× molar excess) ofcalcium in Arab-D brine.

Due to the relatively higher concentration of sulfate ions in seawater,there is a limit to calcium ions that can be added to seawater beforecalcium sulfate would precipitate. In FIG. 8, the calcium concentrationand nanoparticle stability is seawater was examined. Synthetic seawaterwas doped with varying amounts of calcium chloride at a concentrationrange between 0.020M and 0.084M, total calcium concentrations. Therewere no observable precipitates of calcium sulfate when the brines werefirst prepared at room temperature. At the end of the 7-day testduration, only samples with the nanoparticles still in suspension weremeasured. Between calcium concentration of 0.020M and 0.031M, thenanoparticles had aggregated and fallen out of suspension. At a totalcalcium concentration of 0.084M, the nanoparticles were stable inseawater, with stability on par with nanoparticles in Arab-D brine (LS).

Example 2. Crosslinked Glycidylate Polyethylenimine (PEI)-CoatedPolystyrenic

Nanoparticles.

Coating Polystyrene (PS) Nanoparticles with 25 kDa Polyethylenimine.

Overview.

To coat the PS nanoparticles with PEI, the ionic interactions betweenanionic SDS and cationic PEI polymer in an aqueous solution was, inpart, relied upon. As illustrated in FIG. 9, the cationic PEI polymerelectrostatically adsorbs on the surface of PS nanoparticles addeddropwise into the PEI solution. Next, the PEI coating was covalentlycrosslinked by adding the bis-epoxide crosslinker, 1,4-Butanedioldiglycidyl ether. Subsequently, the nanoparticles were treated withglycidol to glycidylate the corona of the nanoparticles to obtain ahighly hydroxylated surface.

Coating.

A stock solution of 25 kDa polyethylenimine (PEI) was first prepared byweighing the appropriate amount of PEI resin in a media bottle. Acetatebuffer (pH 5, 0.7 mL glacial acetic acid and 0.6 g potassium hydroxideper liter) was added to the media bottle as a solvent to constitute 100mg/mL final concentration. For example, for a typical prep of PEI stocksolution, 20 g of PEI resin was weighed into a media bottle that wassubsequently filled with ˜200 mL of acetate buffer and homogenized.

10 mL of 1.7 wt. % 15 nm polystyrene (PS) nanoparticles with sodiumdodecyl sulfate surfactant on the surface was diluted into 10 mLdeionized water and placed in an addition funnel. In a round-bottomflask, 10 mL of 100 mg/mL stock PEI solution was diluted into 10 mL pH 5acetate buffer and magnetically stirred at 500 rotations per minute(RPM). Into the PEI solution, PS nanoparticles were added dropwise usingthe addition funnel. Residual PS suspension in the funnel was rinsedwith a small amount of deionized water and added to the PEI solution.The clear suspension obtained at the completion of the addition step wasstirred overnight.

For the crosslinking step, the PEI-coated nanoparticles were firstcollected and the pH was adjusted to approximately 8 using 1.0Mhydrochloric acid and placed in an addition funnel. 1 mL of1,4-butanediol diglycidyl ether was added to 20 mL of deionized water ina round-bottom flask and homogenized with magnetic stirring at 500 RPM.Under this stirring rate, the PEI-coated nanoparticle solution in theaddition funnel was added dropwise into the crosslinker solution. Uponcompletion of addition, the solution was stirred overnight. To quenchthe reaction, 10 mL of 2.0M tris buffer was added to the solution andleft stirring for 1 hour before the cleaning step.

To remove free PEI and excess reagents from the nanoparticle solution,tangential flow filtration via 100 kDa MWCO filters was performed. For atypical prep described above, yielding approximately 75 mL nanoparticlesolution, approximately 400 mL deionized water was used to clean thenanoparticles. The condition for tangential flow filtration was atapproximately 2 pounds per square inch (psi) transmembrane pressure with25 mL/min feed rate. Two 100 kDa hollow fiber filters were attached intandem to increase throughput of the filtration process.

The purified nanoparticles were first re-concentrated on the tangentialflow filtration set-up to approximately 50 mL and furtherre-concentrated to approximately 20 mL using centrifugal devices with 10kDa MWCO on the centrifuge.

Glycidylation of Crosslinked-PEI Coated PS Nanoparticles

To glycidylate 20 mL of the PEI-coated nanoparticles prepared above, 2mL of glycidol was added into the nanoparticle solution and stirredovernight. To quench the reaction, 5 mL of 2.0M tris buffer was added tothe solution and allowed to stir for at least 1 hour before thepurification step.

Purification of 20 mL glycidylated nanoparticles was accomplished bywashing in deionized water using 100 kDa MWCO centrifugal devices. Thematerials were centifuged at 5000 g for 30 minutes. Filtrates werediscarded and fresh deionized water was added to the retentate. Thepurification procedure was repeated three times.

The collected nanoparticles had pH of approximately 9. The pH wasadjusted to a pH of approximately 6.5 using 37 wt. % hydrochloric acidbefore colloidal stability studies in brine were conducted.

Colloidal Stability Test Protocol

Overview.

To ascertain the stability of the coated nanoparticles in various brinesat high temperatures, 1000 ppm nanoparticle suspensions were prepared insynthetic seawater, synthetic seawater with additional calcium ions (50mM total calcium concentration), and low salinity Arab-D brine. Thenanoparticles suspensions were heat treated in an oven at 90° C. for 14days and their hydrodynamic diameter characterized periodically bydynamic light scattering. The results are depicted in FIG. 10. Over thetwo-week period, the nanoparticles size remained under 25 nm in allthree brine solutions.

Solution Preparation.

10 mL of 1000 ppm nanoparticle suspensions was prepared in syntheticseawater, synthetic seawater with 50 mM calcium chloride, and Arab-Dbrine by diluting the stock 75,000 ppm (approximately 75 mg/mL) solutioninto the brine solutions in glass vials. The vials were crimped withaluminum caps with rubber septa. Each solution was degassed for 5minutes and a 3 mL aliquot of each of the samples was drawn with asyringe and loaded into separate quartz cuvettes with PTFE lined caps.The remainder of the solutions was reserved as room temperaturecontrols.

Static Stability Test.

Before the samples were placed in the oven at 90° C., dynamic lightscattering (DLS) size distribution was recorded. Over 14 days, sampleswere removed periodically from the oven for DLS size distributionmeasurements after they cooled to ambient temperature. After eachmeasurement, the samples were returned to the oven.

Dynamic Light Scattering (DLS).

All samples were measured at 1000 ppm without filtration or dilution.For each sample, three measurements at three minutes acquisition timewere taken. No adjustments in solution viscosity in the measurementparameters were made for the samples in brine.

OTHER EMBODIMENTS

It is to be understood that while the invention has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate and not limit the scope of theinvention, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims.

What is claimed is:
 1. A method of treating a subterranean formation,comprising placing in a subterranean formation: a compositioncomprising: an ion; and a coated nanoparticle comprising: ananoparticle; and a linker comprising an anchoring group, a spacer, anda terminal group, wherein the anchoring group is covalently bound to thenanoparticle, and wherein the terminal group is covalently bound to astabilizing group comprising a functional group selected from the groupconsisting of:

and combinations thereof; and a kosmotropic ion, a chaotropic ion, orcombination thereof.
 2. The method of claim 1, wherein the compositioncomprises an aqueous liquid.
 3. The method of claim 2, wherein theaqueous liquid comprises water, brine, produced water, flowback water,brackish water, fresh water, Arab-D-brine, sea water, mineral waters, orany combination thereof.
 4. The method of claim 1, wherein the coatednanoparticle has a lower critical solution temperature of greater than90° C.
 5. The method of claim 1, wherein the nanoparticle comprises of asilica nanoparticle, a metal oxide nanoparticle, an upconvertingnanoparticle, a superparamagnetic nanoparticle, or any combinationsthereof.
 6. The method of claim 1, wherein the nanoparticle comprises ametal oxide.
 7. The method of claim 1, wherein the nanoparticlecomprises a superparamagnetic metal oxide.
 8. The method of claim 1,wherein the nanoparticle is a silica nanoparticle.
 9. The method ofclaim 1, wherein the nanoparticle has a particle size of about 10nanometers (nm) to about 100 nm.
 10. The method of claim 1, wherein theanchoring group is a silane.
 11. The method of claim 1, wherein thelinker comprises polyethylenimine.
 12. The method of claim 1, whereinthe nanoparticle covalently bound to the linker is obtained by reactingtrimethoxysilylpropyl modified polyethylenimine with the nanoparticle.13. The method of claim 1, wherein the ion comprises at least one of alithium ion, a sodium ion, a potassium ion, a silver ion, a magnesiumion, a calcium ion, a barium ion, a zinc ion, an aluminum ion, a bismuthion, a copper (I) ion, a copper (II) ion, an iron (II) ion, an iron(III) ion, a tin (II) ion, a tin (IV) ion, a chromium (II) ion, achromium (III) ion, a manganese (II) ion, a manganese (III) ion, amercury (I) ion, a mercury (II) ion, a lead (II) ion, a lead (IV) ion, acobalt (II) ion, a cobalt (III) ion, a nickel ion (II), a nickel (IV)ion, a titanium ion, or a titanium (IV) ion.
 14. The method of claim 1,wherein the ion comprises a calcium ion.
 15. The method of claim 1,comprising obtaining or providing the composition, wherein the obtainingor providing of the composition occurs above-surface or in thesubterranean formation.
 16. The method of claim 15, wherein theproviding or obtaining the composition comprises determining presenceand concentration of at least one ion of a water in the subterraneanformation and doping the composition with the determined ion.
 17. Themethod of claim 16, wherein doping the composition with the determinedion comprises increasing an amount of the determined ion in thecomposition such that molarity of the determined ion in the compositionis at least 10% of the molarity of the at least one ion of the water inthe subterranean formation.
 18. The method of claim 1, wherein thekosmotropic ion causes aggregation and precipitation of the coatednanoparticles in the subterranean formation.
 19. The method of claim 1,wherein the kosmotropic ion is selected from the group consisting of asulfate, a phosphate, Mg²⁺, Li⁺, a hydrogenphosphate salt, an ammoniumsulfate, a sodium sulfate, a citrate, and an oxalate.
 20. The method ofclaim 1, wherein the kosmotropic ion is placed in the subterraneanformation prior to, simultaneously with, or after placing thecomposition in the subterranean formation.
 21. The method of claim 1,wherein the composition comprises the kosmotropic ion.
 22. The method ofclaim 1, wherein the chaotropic ion is selected from the groupconsisting of urea, guanidinium chloride, and lithium perchlorate. 23.The method of claim 1, wherein the chaotropic ion is placed in thesubterranean formation prior to, simultaneously with, or after placingthe composition in the subterranean formation.
 24. The method of claim1, wherein the composition comprises the chaotropic ion.